U.S. patent application number 14/865353 was filed with the patent office on 2016-04-14 for temporary bonding laminates for used in manufacture of semiconductor devices and methods for manufacturing semiconductor devices.
This patent application is currently assigned to FUJIFILM Corporation. The applicant listed for this patent is FUJIFILM Corporation. Invention is credited to Yu IWAI, Ichiro KOYAMA.
Application Number | 20160104635 14/865353 |
Document ID | / |
Family ID | 51624402 |
Filed Date | 2016-04-14 |
United States Patent
Application |
20160104635 |
Kind Code |
A1 |
KOYAMA; Ichiro ; et
al. |
April 14, 2016 |
TEMPORARY BONDING LAMINATES FOR USED IN MANUFACTURE OF
SEMICONDUCTOR DEVICES AND METHODS FOR MANUFACTURING SEMICONDUCTOR
DEVICES
Abstract
Provided is temporary bonding laminates for used in a
manufacture of semiconductor devices, by which a member to be
processed can be temporarily supported securely and readily during
a mechanical or chemical process of the member to be processed and
then the processed member can be readily released from the
temporary support without damaging the processed member even after
a high temperature process, and processes for manufacturing
semiconductor devices. The temporary bonding laminate includes
comprising (A) a release layer and (B) an adhesive layer wherein
the release layer (A) comprises (a1) a resin 1 having a softening
point of 200.degree. C. or more and (a2) a resin 2; the resin 2
after curing has capable of being dissolved at 5% by mass or more,
at 25.degree. C., in at least one of solvents selected from hexane
and the like.
Inventors: |
KOYAMA; Ichiro;
(Haibara-gun, JP) ; IWAI; Yu; (Haibara-gun,
JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
FUJIFILM Corporation |
Tokyo |
|
JP |
|
|
Assignee: |
FUJIFILM Corporation
Tokyo
JP
|
Family ID: |
51624402 |
Appl. No.: |
14/865353 |
Filed: |
September 25, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
PCT/JP2014/058723 |
Mar 27, 2014 |
|
|
|
14865353 |
|
|
|
|
Current U.S.
Class: |
438/795 ;
428/352 |
Current CPC
Class: |
H01L 2221/68327
20130101; H01L 21/324 20130101; H01L 2221/68381 20130101; C09J
2301/312 20200801; H01L 21/6835 20130101; C09J 2203/326 20130101;
H01L 2221/6834 20130101; C09J 7/40 20180101; H01L 2221/68318
20130101 |
International
Class: |
H01L 21/683 20060101
H01L021/683; H01L 21/324 20060101 H01L021/324 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 27, 2013 |
JP |
2013-066656 |
Claims
1. A temporary bonding laminate for used in a manufacture of
semiconductor devices, comprising (A) a release layer and (B) an
adhesive layer, wherein the release layer (A) comprises (a1) a
resin 1 having a softening point of 200.degree. C. or more and (a2)
a resin 2; the resin 2 after curing has capable of being dissolved
at 5% by mass or more, at 25.degree. C., in at least one of
solvents selected from hexane, heptane, ethyl acetate, acetone,
methanol, ethanol, isopropanol, 1,4-dioxane, tetrahydrofuran,
1-methoxy-2-propanol, 2-acetoxy-1-methoxypropane, acetonitrile,
methyl ethyl ketone, cyclohexanone, toluene, dimethyl sulfoxide,
N,N-dimethylformamide, N,N-dimethylacetamide,
N-methyl-2-pyrrolidinone, N-ethyl-2-pyrrolidinone, chloroform,
methylene chloride, anisole, xylene, and mesitylene.
2. The temporary bonding laminate for used in a manufacture of
semiconductor devices according to claim 1, wherein the resin 1 has
a softening point in the range of 200.degree. C. to 450.degree.
C.
3. The temporary bonding laminate for used in a manufacture of
semiconductor devices according to claim 1, wherein the resin 1 is
a thermoplastic resin.
4. The temporary bonding laminate for used in a manufacture of
semiconductor devices according to claim 3, wherein the
thermoplastic resin is at least one thermoplastic resin selected
from polyether sulfone resins, polyimide resins, polyester resins,
polybenzimidazole resins, polyphenylene ether resins, polyphenylene
sulfide resins and polyether ketone resins.
5. The temporary bonding laminate for used in a manufacture of
semiconductor devices according to claim 1, wherein the resin 2
comprises a thermoplastic resin selected from polycarbonate resins,
polyurethane resins and hydrocarbon resins.
6. The temporary bonding laminate for used in a manufacture of
semiconductor devices according to claim 1, wherein the resin 1 and
the resin 2 have a difference between SP values [MPa.sup.1/2] of 1
or more and less than 10.
7. The temporary bonding laminate for used in a manufacture of
semiconductor devices according to claim 1, wherein the adhesive
layer (B) comprises a binder, a polymerizable monomer, and at least
one of a photoinitiator and a thermal polymerization initiator.
8. A method for manufacturing a semiconductor device, comprising:
bonding a first surface of a member to be processed and a substrate
via the temporary bonding laminate for used in a manufacture of
semiconductor devices according to claim 1; subjecting the member
to be processed to a heat treatment having a maximum attainable
temperature in the range of 180.degree. C. to 370.degree. C. to
give a processed member; and debonding the processed member from
the temporary bonding laminate; wherein the resin 1 has a softening
point higher than a maximum attainable temperature in the heat
treatment.
9. The method for manufacturing a semiconductor device according to
claim 8, further comprising irradiating the adhesive layer of the
temporary bonding laminate with active rays or radiation or heat
before bonding the first surface of the member to be processed and
the substrate via the temporary bonding laminate.
10. The method for manufacturing a semiconductor device according
to claim 8, further comprising removing the temporary bonding
laminate remaining on the processed member with a stripping solvent
after debonding the member to be processed from the temporary
bonding laminate.
11. The method for manufacturing a semiconductor device according
to claim 10, wherein the stripping solvent comprises at least one
of a hydrocarbon solvent and an ether solvent.
12. The method for manufacturing a semiconductor device according
to claim 11, wherein the stripping solvent comprises at least one
of cyclopentane, n-hexane, cyclohexane, n-heptane, limonene,
p-menthane, tetrahydrofuran (THF), 1,3-dioxolane, and anisole.
13. The temporary bonding laminate for used in a manufacture of
semiconductor devices according to claim 2, wherein the resin 1 is
a thermoplastic resin.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a Continuation of PCT International
Application No. PCT/JP2014/058723 filed on Mar. 27, 2014, which
claims priority under 35 U.S.C .sctn.119(a) to Japanese Patent
Application No. 2013-066656 filed on Mar. 27, 2013. Each of the
above application(s) is hereby expressly incorporated by reference,
in its entirety, into the present application.
TECHNICAL FIELD
[0002] The present invention relates to temporary bonding laminates
for used in a manufacture of semiconductor devices and processes
for manufacturing semiconductor devices.
BACKGROUND ART
[0003] Conventional manufacturing processes of semiconductor
devices such as ICs and LSIs typically comprise forming a number of
IC chips on a semiconductor silicon wafer and singulating it by
dicing.
[0004] The demand for smaller electronic equipment with higher
performance also leads to a demand for smaller IC chips with a
higher degree of integration incorporated into the electronic
equipment, but the density of integrated circuits in the direction
of the plane of silicon substrates is close to the limit.
[0005] Wire bonding is a conventionally widely known technique for
electrically connecting integrated circuits in IC chips to external
terminals of the IC chips, and an alternative technique suitable
for smaller IC chips has also recently been known, which comprises
forming through-holes in a silicon substrate and connecting metal
plugs as external terminals to integrated circuits via the
through-holes (so-called, a method of forming a through-silicon
electrode (TSV)). However, the technique comprising forming
through-silicon vias alone cannot sufficiently meet the recent
demand for IC chips with a higher degree of integration.
[0006] To overcome the drawbacks described above, a technique is
known for improving the degree of integration per unit area of
silicon substrates by providing multilayer integrated circuits in
IC chips. However, the multilayer integrated circuits increase the
thickness of the IC chips so that components of the IC chips must
be thinned. Such components suggested to be thinned include, for
example, silicon substrates, and this is a promising solution
because it allows not only for reducing the size of IC chips but
also for saving labor in the step of forming through-holes in
silicon substrates during the preparation of through-silicon
vias.
[0007] The semiconductor silicon wafer used in a method for
manufacturing semiconductor device, are widely known to have a
thickness of about 700 to 900 .mu.m. Recently, for the purpose of
miniaturization or the like of an IC chip, it has been attempted to
reduce the thickness of the semiconductor silicon wafer to be 200
.mu.m or less. To reduce the size of IC chips or for other
purposes, attempts have recently been made to reduce the thickness
of semiconductor silicon wafers to be 200 .mu.m or less.
[0008] However, semiconductor silicon wafers having a thickness of
200 .mu.m or less are so thin and therefore, components for
manufacturing semiconductor devices using them as base materials
are also so thin that such components are hard to stably support
without damaging them during further processing or simply
transferring or otherwise handling such components.
[0009] To solve the problems as described above, a known technique
comprises temporarily bonding an unthinned semiconductor wafer
having devices on its surface to a supporting substrate for
processing using a silicone adhesive; thinning the semiconductor
wafer by backgrinding; then drilling the semiconductor wafer to
form through-silicon vias; and then debonding the supporting
substrate for processing from the semiconductor wafer (see patent
document 1). It is said that this technique allows for achieving
resistance to grinding during backgrinding of the semiconductor
wafer, heat resistance during an anisotropic dry etching process or
the like, chemical resistance during plating or etching, smooth
separation from the supporting substrate for processing at the
final stage and low contamination on the wafer at the same
time.
[0010] A technique for supporting a wafer by a carrier layer system
is also known, comprising inserting a plasma polymer layer obtained
by plasma deposition as a separation layer between the wafer and
the carrier layer system in such a manner that the bond strength
between the carrier layer system and the separation layer is
greater than the bond strength between the wafer and the separation
layer, whereby the wafer is readily debonded from the separation
layer when the wafer is debonded from the carrier layer system (see
patent document 2).
[0011] Another known technique comprises a temporary bonding step
using a polyether sulfone and a tackifier, and a debonding step by
heating (patent document 3).
[0012] Another known technique comprises a temporary bonding step
using a mixture of a carboxylic acid and an amine, and a debonding
step by heating (patent document 4).
[0013] Another known technique comprises bonding a device wafer and
a carrier substrate under pressure via a heated bonding layer
formed of a cellulose polymer or the like, and debonding the device
wafer from the carrier substrate by heating and sliding apart them
in a transverse direction (patent document 5).
[0014] Further, an adhesive film comprising syndiotactic
1,2-polybutadiene and a photoinitiator is known, wherein the bond
strength of the film can be changed by irradiation (patent document
6).
[0015] Another known technique comprises temporarily bonding a
carrier substrate and a semiconductor wafer using an adhesive
formed of a polycarbonate, processing the semiconductor wafer, then
irradiating it, and then debonding the processed semiconductor
wafer from the carrier substrate by heating (patent document
7).
[0016] Further, a known technique for temporarily bonding a device
surface of a device wafer having microdevices and a carrier
substrate supporting the device wafer comprises temporarily bonding
a peripheral region of the device surface and the carrier substrate
with an adhesive via a fill layer not participating in bonding
inserted between a central region of the device surface and the
carrier substrate (patent document 8).
REFERENCES
Patent Documents
[0017] Patent document 1: JPA2011-119427; [0018] Patent document 2:
JPA2009-528688; [0019] Patent document 3: JPA2011-225814; [0020]
Patent document 4: JPA2011-052142; [0021] Patent document 5:
JPA2010-506406; [0022] Patent document 6: JPA2007-045939; [0023]
Patent document 7: US Patent Application Publication No.
2011/0318938; [0024] Patent document 8: JPA2011-510518.
SUMMARY OF THE INVENTION
Problems to be Solved by the Invention
[0025] When a surface of a semiconductor wafer having devices
(i.e., a device surface of a device wafer) and a supporting
substrate (carrier substrate) are to be temporarily bonded via a
layer formed of an adhesive known from patent document 1 or the
like, the adhesive layer must have enough adhesiveness to stably
support the semiconductor wafer. Thus, when the entire device
surface of a semiconductor wafer and a supporting substrate are to
be temporarily bonded via an adhesive layer, the following problem
is likely to occur: the temporary bond between the semiconductor
wafer and the supporting substrate must be enough strong to stably
support the semiconductor wafer without damaging it, but the
temporary bond between the semiconductor wafer and the supporting
substrate is so strong that devices may be broken or separated from
the semiconductor wafer when the semiconductor wafer is debonded
from the supporting substrate.
[0026] Further, the method comprising forming a plasma polymer
layer as a separation layer by plasma deposition between a wafer
and a carrier layer system to prevent the wafer and the carrier
layer system from being bonded too strongly as described in patent
document 2 has the following drawbacks: (1) the equipment for
performing plasma deposition typically requires much cost; (2) the
layer formation by plasma deposition requires a considerable time
for evacuation in a plasma deposition system or deposition of a
monomer; and (3) even if a separation layer formed of a plasma
polymer layer is inserted, it is not easy to control the bond
strength in such a manner that the bond strength between the wafer
and the separation layer is enough when the wafer to be processed
is supported, while the wafer is readily debonded from the
separation layer when the wafer is released from the support.
[0027] Further, the method comprising a debonding step by heating
as described in patent documents 3, 4 and 5 is likely to encounter
the problem that devices may be broken by lengthy heating.
[0028] Further, the method comprising a debonding step by
irradiation as described in patent documents 6 and 7 necessitates
the use of a radiation-transparent carrier substrate.
[0029] Further, the method comprising inserting a fill layer not
participating in bonding on a carrier as described in patent
document 8 must comprise a multistage process for forming the fill
layer, and therefore it should be further improved in
productivity.
[0030] The present invention was made under the circumstances
described above, and aims to provide temporary bonding laminates
for used in a manufacture of semiconductor devices, by which a
member to be processed (a semiconductor wafer or the like) can be
temporarily supported securely and readily during a mechanical or
chemical process of the member to be processed and then the
processed member can be readily released from the temporary support
without damaging the processed member even after a high temperature
process, and processes for manufacturing semiconductor devices.
Means for Solving the Problems
[0031] As a result of our careful studies to solve the problems
described above, we achieved the present invention on the basis of
the finding that if a temporary bonding laminate comprising a
release layer and an adhesive layer is provided between a support
and a member to be processed wherein the release layer comprises a
resin having a specific softening point and a solvent-soluble
resin, the processed member can be readily released from the
temporary support even after a high temperature process.
[0032] Specifically, the problems were solved by the solving means
<1>, preferably by solving means <2>to <12>below.
[0033] <1>A temporary bonding laminate for used in a
manufacture of semiconductor devices, comprising (A) a release
layer and (B) an adhesive layer, wherein the release layer (A)
comprises (a1) a resin 1 having a softening point of 200.degree. C.
or more and (a2) a resin 2; the resin 2 after curing has capable of
being dissolved at 5% by mass or more, at 25.degree. C., in at
least one of solvents selected from hexane, heptane, ethyl acetate,
acetone, methanol, ethanol, isopropanol, 1,4-dioxane,
tetrahydrofuran, 1-methoxy-2-propanol, 2-acetoxy-1-methoxypropane,
acetonitrile, methyl ethyl ketone, cyclohexanone, toluene, dimethyl
sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide,
N-methyl-2-pyrrolidinone, N-ethyl-2-pyrrolidinone, chloroform,
methylene chloride, anisole, xylene, and mesitylene. [0034]
<2>The temporary bonding laminate for used in a manufacture
of semiconductor devices according to <1>, wherein the resin
1 has a softening point in the range of 200.degree. C. to
450.degree. C. [0035] <3>The temporary bonding laminate for
used in a manufacture of semiconductor devices according to
<1>or <2>, wherein the resin 1 is a thermoplastic
resin. [0036] <4>The temporary bonding laminate for used in a
manufacture of semiconductor devices according to <3>,
wherein the thermoplastic resin is at least one thermoplastic resin
selected from polyether sulfone resins, polyimide resins, polyester
resins, polybenzimidazole resins, polyphenylene ether resins,
polyphenylene sulfide resins and polyether ketone resins. [0037]
<5>The temporary bonding laminate for used in a manufacture
of semiconductor devices according to any one of <1>to
<4>, wherein the resin 2 comprises a thermoplastic resin
selected from polycarbonate resins, polyurethane resins and
hydrocarbon resins. [0038] <6>The temporary bonding laminate
for used in a manufacture of semiconductor devices according to any
one of <1>to <5>, wherein the resin 1 and the resin 2
have a difference between SP values [MPa.sup.1/2] of 1 or more and
less than 10. [0039] <7>The temporary bonding laminate for
used in a manufacture of semiconductor devices according to anyone
of <1>to <6>, wherein the adhesive layer (B) comprises
a binder, a polymerizable monomer, and at least one of a
photoinitiator and a thermal polymerization initiator. [0040]
<8>A method for manufacturing a semiconductor device,
comprising: bonding a first surface of a member to be processed and
a substrate via the temporary bonding laminate for used in a
manufacture of semiconductor devices according to any one of
<1>to <7>; subjecting the member to be processed to a
heat treatment having a maximum attainable temperature in the range
of 180.degree. C. to 370.degree. C. to give a processed member; and
debonding the processed member from the temporary bonding laminate;
wherein the resin 1 has a softening point higher than a maximum
attainable temperature in the heat treatment. [0041] <9>The
method for manufacturing a semiconductor device according to
<8>, further comprising irradiating the adhesive layer of the
temporary bonding laminate with active rays or radiation or heat
before bonding the first surface of the member to be processed and
the substrate via the temporary bonding laminate. [0042]
<10>The method for manufacturing a semiconductor device
according to <8>or <9>, further comprising removing the
temporary bonding laminate remaining on the processed member with a
stripping solvent after debonding the member to be processed from
the temporary bonding laminate. [0043] <11>The method for
manufacturing a semiconductor device according to <10>,
wherein the stripping solvent comprises at least one of a
hydrocarbon solvent and an ether solvent. [0044] <12>The
method for manufacturing a semiconductor device according to
<11>, wherein the stripping solvent comprises at least one of
cyclopentane, n-hexane, cyclohexane, n-heptane, limonene,
p-menthane, tetrahydrofuran (THF), 1,3-dioxolane, and anisole.
Advantages of the Invention
[0045] The present invention makes it possible to provide temporary
bonding laminates for used in a manufacture of semiconductor
devices, by which a member to be processed can be temporarily
supported securely and readily during a mechanical or chemical
process of the member to be processed and then the processed member
can be readily released from the temporary support without damaging
the processed member even after a high temperature process, and
processes for manufacturing semiconductor devices.
BRIEF EXPLANATION OF THE DRAWINGS
[0046] FIG. 1A is a schematic diagram showing how a solvent
permeates through a release layer according to the present
invention and, FIG. 1B is a schematic diagram showing how a solvent
permeates through a release layer according to the prior art.
[0047] FIG. 2 is a schematic diagram of a solvent shows a state of
penetrating the surface of the release layer in the present
invention.
[0048] FIG. 3A, FIG. 3B and FIG. 3C are a schematic sectional view
illustrating how to temporarily bond an adhesive support and a
device wafer, a schematic sectional view showing the device wafer
temporarily bonded to the adhesive support, and a schematic
sectional view showing the device wafer temporarily bonded to the
adhesive support after it has been thinned, respectively.
[0049] FIG. 4 is a schematic top view of an adhesive support
according to the present invention.
[0050] FIG. 5 is a schematic top view of an adhesive support
according to the present invention.
[0051] FIG. 6 is a schematic top view of an adhesive support
according to an embodiment of the present invention.
[0052] FIG. 7 is a schematic top view of an adhesive support
according to an embodiment of the present invention.
[0053] FIG. 8 is a schematic top view of an adhesive support
according to an embodiment of the present invention.
[0054] FIG. 9 is a schematic top view of an adhesive support
according to an embodiment of the present invention.
[0055] FIG. 10 is a schematic top view of an adhesive support
according to an embodiment of the present invention.
[0056] FIG. 11 is a schematic top view of an adhesive support
according to an embodiment of the present invention.
[0057] FIG. 12 is a schematic top view of an adhesive support
according to an embodiment of the present invention.
[0058] FIG. 13 is a schematic top view of an adhesive support
according to an embodiment of the present invention.
[0059] FIG. 14 is a schematic top view of an adhesive support
according to an embodiment of the present invention.
[0060] FIG. 15 is a schematic sectional view illustrating how an
adhesive support and a device wafer are released from a temporary
bond according to a prior art.
DESCRIPTION OF EMBODIMENTS
[0061] The present invention will be explained in detail below. In
this specification, notation of group (atomic group) without being
preceded by "substituted" or "unsubstituted", is used to encompass
not only group having no substituent, but also group having
substituent. For example, "alkyl group" encompass not only alkyl
group having no substituent (unsubstituted alkyl group), but also
alkyl group having substituent (substituted alkyl group). In the
present specification, the term "monomer" and "monomer" is
synonymous.
[0062] In this specification, "actinic rays" and "radiation" means,
for example, those with visible light, ultraviolet light, far
ultraviolet rays, electron beams, X-rays or the like. Further, in
the present invention, "light", it means actinic rays or
radiation.
[0063] In this specification, "exposure", unless otherwise
indicated, exposure with far ultraviolet rays typified by mercury
lamp, ultraviolet rays, excimer laser, X-ray, EUV light or the
like, and a drawing with a particle beam such as an electron beam
and ion beam.
[0064] In this specification, "(meth)acrylate" means acrylate and
methacrylate, "(meth)acryl" means acryl and methacryl,
"(meth)acryloyl" means acryloyl and methacryloyl. The monomer in
the present invention is discriminated from oligomer and polymer,
and means any compound having a weight-average molecular weight of
2,000 or smaller. In this specification, the polymerizable compound
means any compound having a polymerizable functional group, and may
be a monomer or polymer. The polymerizable functional group means
any group participating a polymerization reaction.
[0065] In the embodiments described below, for the members and the
like described in the previously referenced drawings are simplified
or omitted of explanation are denoted by the same reference
numerals or corresponding reference numerals in the figures.
[0066] The temporary bonding laminates for used in the manufacture
of semiconductor devices according to the present invention
(hereinafter also simply referred to as "temporary bonding
laminates") comprise (A) a release layer and (B) an adhesive layer,
wherein the release layer (A) comprises (a1) a resin 1 having a
softening point of 200.degree. C. or more, and (a2) a resin 2
capable of being dissolved at 5% by mass or more in at least one of
solvents selected from hexane, heptane, ethyl acetate, acetone,
methanol, ethanol, isopropanol, 1,4-dioxane, tetrahydrofuran,
1-methoxy-2-propanol, 2-acetoxy-1-methoxypropane, acetonitrile,
methyl ethyl ketone, cyclohexanone, toluene, dimethyl sulfoxide,
N,N-dimethylformamide, N,N-dimethylacetamide,
N-methyl-2-pyrrolidinone, N-ethyl-2-pyrrolidinone, chloroform,
methylene chloride, anisole, xylene, and mesitylene at 25.degree.
C. after curing (hereinafter sometimes referred to as
"solvent-soluble"). In the present invention, the permeation of
solvents into the release layer is promoted by incorporating the
solvent-soluble resin into the release layer. This concept is
explained with reference to FIG. 1 and FIG. 2.
[0067] FIG. 1 is a schematic diagram showing how a solvent
permeates through a release layer according to the present
invention and the prior art, wherein 1 represents a release layer
and 2 represents a resin 2, respectively. Further, the straight and
wavy lines with arrowheads in the figure indicate how the solvent
permeates. It should be noted that FIG. 1 serves only for a better
understanding of the concept of the present invention, and the
amount of the resin 2 (designated by 2 in the figure) and the size
of the resin 2 (designated by 2 in the figure) in the release layer
are not limited to those shown in FIG. 1 (as well as the other
drawings).
[0068] According to the present invention, the resin 2 (designated
by 2 in the figure) exists in the release layer 1, i.e., a layer
comprising the resin 1 as a main component, as shown in FIG. 1A. It
is shown as spheres in FIG. 1, but it may not necessarily be in
such a shape. When a solvent enters into the release layer as shown
by the arrow in FIG. 1A, the solvent slowly permeates through the
resin 1 as shown by the wavy lines with arrowheads, but rapidly
permeates through the resin 2 so that the resin 2 dissolves in the
solvent earlier. If the resin 2 dissolves, the solvent also readily
permeates through the resin 1 whereby the layer as a whole
dissolves in the solvent more readily. However, the solvent slowly
permeated through the conventional release layer because a binder
existed alone in it without any material such as the resin 2, as
shown in FIG. 1B. Such a difference in structure allows the resin 1
in the release layer of the present invention to be separated
readily, whereby the release layer can be separated readily.
[0069] According to an alternative embodiment of the present
invention, the resin 2 may exist on the surface of the release
layer 1, as shown in FIG. 2. In this embodiment, the surface area
of the release layer 1 into which the solvent enters increases. As
a result, the solvent permeates into the release layer more
readily, whereby the release layer can be separated more
readily.
[0070] A temporary bonding laminate for used in a manufacture of
semiconductor devices of the present invention is explained
hereinafter.
[0071] The temporary bonding laminates for used in a manufacture of
semiconductor devices according to the present invention are
preferably used in a manufacture of semiconductor devices
comprising performing a heat treatment.
[0072] The temporary bonding laminates for used in a manufacture of
semiconductor devices according to the present invention provide
temporary bonding laminates for used in a manufacture of
semiconductor devices, by which a member to be processed can be
temporarily supported securely and readily during a mechanical or
chemical process of the member to be processed and then the
processed member can be readily released from the temporary support
without damaging the processed member even after a high temperature
process.
[0073] The temporary bonding laminates for used in a manufacture of
semiconductor devices according to the present invention are
preferably used for forming through-silicon vias. The formation of
through-silicon vias will be explained in detail later.
<(A) Release Layer>
[0074] The release layer (A) according to the present invention
comprises (a1) a resin 1 having a softening point of 200.degree. C.
or more, and (a2) a resin 2 that will be solvent-soluble after
curing.
<<Resin 1>>
[0075] The resin 1 is used for the purpose of improving the ease of
release from the surface of the release layer. Therefore, the resin
1 should have releasability less influenced by heat. The resin 1
has a softening point of 200.degree. C. or more. Preferably, the
softening point is 200.degree. C. to 450.degree. C., more
preferably 250.degree. C. to 400.degree. C., even more preferably
280.degree. C. to 350.degree. C. In this connection, the softening
point of the resin 1 refers to the value measured by a conventional
method using a viscoelastometer.
[0076] The softening point of the resin 1 is determined as the
temperature at which the loss tangent (tan .delta.) measured using
a viscoelastometer under predetermined heating conditions is
maximum.
[0077] The loss tangent (tan .delta.) is calculated by the equation
below:
[0078] The softening point of the resin 1 is determined as the
temperature at which the loss tangent (tan .delta.) measured using
a viscoelastometer under predetermined heating conditions is
maximum.
[0079] The loss tangent (tan .delta.) is calculated by the equation
below:
tan .delta.=G''/G'
[0080] wherein G'' represents shear loss modulus, and G' represents
shear storage modulus.
[0081] The heating rate is preferably in the range of 0.5 to
20.degree. C./min, more preferably in the range of 1 to 10.degree.
C./min, especially preferably in the range of 2 to 5.degree.
C./min.
[0082] Examples of the resin 1 include synthetic resins such as
olefin copolymers (e.g., methylpentene copolymers), cycloolefin
copolymers (e.g., norbornene copolymers, dicyclopentadiene
copolymers, tetracyclododecene copolymers), novolac resins,
phenolic resins, epoxy resins, melamine resins, urea resins,
unsaturated polyester resins, alkyd resins, polyurethane resins,
solvent-soluble polyimide resins, polyethylene resins,
polypropylene resins, polyvinyl chloride resins, polyvinyl acetate
resins, PTFE resins, PFA resins, FEP resins, ethylene-TFE copolymer
resins, PVDF resins, PCTFE resins, ethylene-CTFE resins,
TFE-perfluorodimethyldioxole copolymer resins, PVF resins, ABS
resins, AS resins, acrylic resins, cellulose resins, polyamides,
polyacetals, polycarbonates, polyphenylene ethers, polybutylene
terephthalates, polyethylene terephthalates, cyclic polyolefins,
polyphenylene sulfides, polysulfones, polyether sulfone resins,
polybenzimidazole resins, polyarylateresins, and polyether ketone
resins; and natural resins such as natural rubbers. Among others,
preferred are PTFE resins, PFA resins, FEP resins, ethylene-TFE
copolymer resins, PVDF resins, PCTFE resins, ethylene-CTFE resins,
TFE-perfluorodimethyldioxole copolymer resins, PVF resins,
polyether sulfone resins, solvent-soluble polyimide resins,
polyester resins, polybenzimidazole resins, polyphenylene ether
resins, and polyether ketone resins, more preferably PFA resins,
TFE-perfluorodimethyldioxole copolymer resins, PVF resins,
polyether sulfone resins, solvent-soluble polyimide resins,
polyester resins, polybenzimidazole resins, polyphenylene ether
resins and polyether ketone resins, especially preferably polyether
sulfone resins, solvent-soluble polyimide resins, polyester resins,
polybenzimidazole resins, polyphenylene ether resins, and polyether
ketone resins.
[0083] Preferably, the resin 1 is a thermoplastic resin, especially
preferably at least one thermoplastic resin selected from polyether
sulfone resins, solvent-soluble polyimide resins, polyester resins,
polybenzimidazole resins, polyphenylene ether resins and polyether
ketone resins.
[0084] The resin 1 according to the present invention typically has
a solvent solubility lower than that of the resin 2. The resin 1
according to the present invention is preferably dissolved in at
least one of the specific solvents mentioned above at 25.degree. C.
after curing at a concentration (% by mass) lower than that of the
resin 2 by 5 to 15% by mass. Further, the resin 1 is preferably
dissolved in at least one of the specific solvents mentioned above
at a concentration (% by mass) of 1 to 50% by mass at 25.degree.
C.
<Resin 2>
[0085] The resin 2 is used for the purpose of improving the removal
of residues of the release layer from the processed member with a
solvent.
[0086] The resin 2 according to the present invention comprises a
resin capable of being dissolved at 5% by mass or more in at least
one of solvents selected from hexane, heptane, ethyl acetate,
acetone, methanol, ethanol, isopropanol, 1,4-dioxane,
tetrahydrofuran, 1-methoxy-2-propanol, 2-acetoxy-1-methoxypropane,
acetonitrile, methyl ethyl ketone, cyclohexanone, toluene, dimethyl
sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide,
N-methyl-2-pyrrolidinone, N-ethyl-2-pyrrolidinone, chloroform,
methylene chloride, anisole, xylene, and mesitylene at 25.degree.
C. after curing. Thus, the resin 2 is used to more easily remove
the resin 1 from the processed member with a solvent.
[0087] Therefore, the resin 2 must comprise a resin that will be
solvent-soluble after curing. More preferably, the solvent-soluble
resin according to the present invention is a resin capable of
being dissolved at 10% by mass or more in at least one of the
solvents mentioned above at 25.degree. C. In such embodiments, the
removal of the release layer can be rapidly completed. Especially,
it would take a long time to remove the release layer according to
the present invention comprising the resin 1 having a high
softening point with a solvent if it were solely formed of a
release layer having a high softening point because such a high
softening point material should be highly cohesive in nature.
[0088] Further, the resin 2 according to the present invention must
be solvent-soluble after curing, but may or may not be
solvent-soluble before curing.
[0089] The resin 2 according to the present invention typically has
a softening point lower than the softening point of the resin 1.
The softening point of the resin 2 according to the present
invention is preferably lower than the softening point of the resin
1 by 20.degree. C. or more, more preferably 50.degree. C. or
more.
[0090] In the present invention, any solvent-soluble resins can be
used as the resin 2.
[0091] For example, they include synthetic resins such as terpene
resins, terpene phenolic resins, modified terpene resins,
hydrogenated terpene resins, hydrogenated terpene phenolic resins,
rosins, rosin esters, hydrogenated rosins, hydrogenated rosin
esters, polymerized rosins, polymerized rosin esters, modified
rosins, rosin-modified phenolic resins, alkyl phenolic resins,
aliphatic petroleum resins, aromatic petroleum resins, hydrogenated
petroleum resins, modified petroleum resins, alicyclic petroleum
resins, coumarone petroleum resins, indene petroleum resins, olefin
copolymers (e.g., methylpentene copolymers), cycloolefin copolymers
(e.g., norbornene copolymers, dicyclopentadiene copolymers,
tetracyclododecene copolymers), unsaturated polyester resins, alkyd
resins, polyurethane resins, solvent-soluble polyimide resins,
polyethylene resins, polypropylene resins, polyvinyl chloride
resins, polystyrene-polymethyl methacrylate resins, polyvinyl
acetate resins, ABS resins, AS resins, acrylic resins, modified
cellulose resins, polyamides, polyacetals, polycarbonates,
polyphenylene ethers, polybutylene terephthalates, polyethylene
terephthalates, cyclic polyolefins, polysulfones, and polyether
sulfone resins; and natural resins such as natural rubbers. Among
others, preferred are terpene resins, terpene phenolic resins,
modified terpene resins, hydrogenated terpene resins, hydrogenated
terpene phenolic resins, rosins, rosin esters, hydrogenated rosins,
hydrogenated rosin esters, polymerized rosins, polymerized rosin
esters, modified rosins, rosin-modified phenolic resins, alkyl
phenolic resins, aliphatic petroleum resins, aromatic petroleum
resins, hydrogenated petroleum resins, modified petroleum resins,
alicyclic petroleum resins, coumarone petroleum resins, indene
petroleum resins, olefin copolymers, cycloolefin copolymers,
polystyrene-polymethyl methacrylate resins, modified cellulose
resins, and polycarbonates, more preferably hydrogenated terpene
resins, cycloolefin copolymers, polystyrene resins,
polystyrene-polymethyl methacrylate resins, and polycarbonates.
[0092] The total amount of the resin 1 and the resin 2 contained in
the release layer of the present invention is preferably 1 to 50%
by mass, more preferably 10 to 40% by mass, especially preferably
20 to 30% by mass of the release layer composition used in the
present invention.
[0093] The ratio by mass between the amounts of the resin 1 and the
resin 2 (resin 1/resin 2) is preferably 99/1 to 50/50, more
preferably 90/10 to 60/40, even more preferably 80/20 to 75/25.
[0094] To stratify the resin 1 and the resin 2 more effectively in
the release layer, the difference between the SP values
[MPa.sup.1/2] of the resin 1 and the resin 2 is preferably 1 or
more and less than 10, more preferably 2 or more and less than 9,
even more preferably 3 or more and less than 8.
[0095] The total amount of resins contained in the release layer of
the present invention is preferably 1 to 100% by mass, more
preferably 70 to 100% by mass, especially preferably 90 to 100% by
mass based on the total solids (i.e., the amount excluding the
solvent) of the release layer of the present invention. The release
layer of the present invention may contain resins other than the
resin 1 and the resin 2 described above without departing from the
spirit of the present invention, but such other resins are
preferably contained in an amount of 5% by mass or less of the
total resin components contained in the release layer.
<<<Solvent>>>
[0096] In the present invention, a solvent is typically used to
form the release layer. Any known solvents that can form the
release layer can be used without limitation, including
N-methyl-2-pyrrolidone, N,N-dimethylacetamide, 2-butanone, methyl
amyl ketone, anisole, xylene and the like, preferably
N-methyl-2-pyrrolidone, N,N-dimethylacetamide, methyl amyl ketone
or anisole.
[0097] The solvents are preferably used in such an amount that the
solids content of the release layer composition for forming the
first release layer is 5 to 40% by mass.
<<<Other Additives>>>
[0098] The first release layer composition may optionally contain
various additives.
[0099] The release layer composition of the present invention may
contain various surfactants to further improve coatability.
Surfactants that can be used include various surfactants such as
fluorosurfactant, nonionic surfactants, cationic surfactants,
anionic surfactants, silicone surfactants and the like.
[0100] Especially when the release layer composition of the present
invention used for the release layer contains a fluorosurfactant,
the liquid properties (especially flowability) of the coating
solution prepared therefrom are further improved so that the
uniformity of the coating thickness and coating consumption
reduction can be further improved.
[0101] In other words, when a coating solution prepared from the
first release layer composition containing a fluorosurfactant is
used to form a film, interfacial tension between the substrate
surface and the coating solution decreases, whereby wettability on
the substrate surface and coatability on the substrate surface are
improved. Thus, such embodiments are effective because a film of an
even and uniform thickness can be formed more suitably even if it
is formed in a small thickness in the order of several micrometers
by using a small amount of the coating solution.
[0102] The fluorine content in the fluorosurfactant is preferably
3% by mass to 40% by mass, more preferably 5% by mass to 30% by
mass, especially preferably 7% by mass to 25% by mass.
Fluorosurfactants having a fluorine content in the ranges indicated
above are effective for obtaining coated films having a uniform
thickness and for reducing coating consumption, and they are also
well soluble in the release layer composition.
[0103] Fluorosurfactants include, for example, Megaface F171, F172,
F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479,
F482, F554, F780, and F781 (all from DIC Corporation); Fluorad
FC430, FC431, and FC171 (all from Sumitomo 3M Limited) ; SURFLON
S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383,
5393, and KH-40 (all from ASAHI GLASS CO., LTD.); PF636, PF656,
PF6320, PF6520, and PF7002 (from OMNOVA) and the like.
[0104] Nonionic surfactants specifically include glycerol,
trimethylolpropane, trimethylolethane as well as ethoxylates and
propoxylates thereof (e.g., glycerol propoxylate, glycerol
ethoxylate and the like); polyoxyethylene lauryl ether,
polyoxyethylene stearyl ether, polyoxyethylene oleyl ether,
polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl
ether, polyethylene glycol dilaurate, polyethylene glycol
distearate, sorbitan fatty acid esters (Pluronic L10, L31, L61,
L62, 10R5, 17R2 and 25R2, and Tetronic 304, 701, 704, 901, 904 and
150R1 from BASF; Solsperse 20000 from Lubrizol Japan Limited) and
the like.
[0105] Cationic surfactants specifically include phthalocyanine
derivatives (available from Morishita Sangyo K.K. under the brand
name EFKA-745); the organosiloxane polymer KP341 (from Shin-Etsu
Chemical Co., Ltd.); the (meth)acrylic (co)polymers POLYFLOW No.
75, No. 90, and No. 95 (from Kyoeisha Chemical Co., Ltd.); W001
(from Yusho Co., Ltd.); and the like.
[0106] Anionic surfactants specifically include W004, W005 and W017
(from Yusho Co., Ltd.) and the like.
[0107] Silicone surfactants include, for example, "Toray Silicone
DC3PA", "Toray Silicone SH7PA", "Toray Silicone DC11PA", "Toray
Silicone SH21PA", "Toray Silicone SH28PA", "Toray Silicone SH29PA",
"Toray Silicone SH3 OPA" , and "Toray Silicone SH8400" from Dow
Corning Toray Co., Ltd.; "TSF-4440", "TSF-4300", "TSF-4445",
"TSF-4460", and "TSF-4452" from Momentive Performance Materials
Inc.; "KP3 41 ", "KF6001", and "KF6002" from Shin-Etsu Silicone,
Co., Ltd.; "BYK307", "BYK323", and "BYK330" from BYK Japan KK; and
the like.
[0108] The surfactants may be used alone or as a combination of two
or more of them.
[0109] The amount of the surfactants to be added is preferably
0.001% by mass to 2.0% by mass, more preferably 0.005% by mass to
1.0% by mass based on the total solids of the release layer
composition.
[0110] The method for forming the release layer of the temporary
bonding laminates for used in a manufacture of semiconductor
devices according to the present invention is not specifically
limited, but can be suitably accomplished by appropriately changing
the types and amounts of resins 1 described above as preferred
examples, i.e., by using a resins 1 and resins 2 selected from the
preferred specific examples indicated above at a more preferred
concentration.
<(B) Adhesive Layer>
[0111] The adhesive layer is used for the purpose of bonding the
release layer and the substrate. Therefore, the adhesive layer
should have adhesiveness less influenced by heat/chemicals.
[0112] The adhesive layer can be formed by applying (preferably
coating) an adhesive composition containing various components
described later on a carrier substrate using a known technique such
as spin coating, spray coating, roller coating, flow coating, blade
coating, dip coating or the like, and then drying it.
[0113] Further, the adhesive layer may be a layer having an
adhesiveness that increases or decreases by irradiation with active
rays or radiation or a layer having two or more regions of
different bond strengths obtained by exposing the surface of a
layer having an adhesiveness that increases or decreases by
irradiation with active rays or radiation.
[0114] Exposure is preferably pattern exposure using a mask,
specifically as described later.
[0115] The thickness of the adhesive layer is, for example, in the
range of 1 to 500 .mu.m, but not specifically limited.
<<Binder>>
[0116] Preferably, the adhesive composition (therefore, the
adhesive layer) contains a binder.
[0117] In the present invention, any binders can be used. For
example, they include synthetic resins such as hydrocarbon resins,
novolac resins, phenolic resins, epoxy resins, melamine resins,
urea resins, unsaturated polyester resins, alkyd resins,
polyurethanes, polyimides, polyethylenes, polypropylenes, polyvinyl
chlorides, polystyrenes, styrene-methyl methacrylate copolymer
resins, polyvinyl acetates, Teflon (registered trademark), ABS
resins, AS resins, acrylic resins, polyamides, polyacetals,
polycarbonates, polyphenylene ethers, polybutylene terephthalates,
polyethylene terephthalates, cyclic polyolefins, polyphenylene
sulfides, polysulfones, polyether sulfones, polyarylates, polyether
ether ketones, and polyamideimides; and natural resins such as
natural rubbers. Among others, preferred are polyurethanes, novolac
resins, polyimides, polystyrenes, and styrene-methyl methacrylate
copolymer resins, more preferably novolac resins, polyimides,
polystyrenes, and styrene-methyl methacrylate copolymer resins,
especially preferably polyimides, polystyrenes, and styrene-methyl
methacrylate copolymer resins.
[0118] In the present invention, any hydrocarbon resins can be
used.
[0119] As used herein, the hydrocarbon resin basically refers to a
resin solely consisting of carbon atoms and hydrogen atoms, but it
may contain other atoms in the side chain so far as its basic
skeleton is a hydrocarbon resin. Further, the hydrocarbon resin as
used herein does not include a resin in which a non-hydrocarbon
functional group is directly attached to the main chain, such as
acrylic resins, polyvinyl alcohol resins, polyvinyl acetal resins,
and polyvinyl pyrrolidone resins.
[0120] Hydrocarbon resins satisfying the criteria described above
include, for example, polystyrene resins, terpene resins, terpene
phenol resins, modified terpene resins, hydrogenated terpene
resins, hydrogenated terpene phenol resins, rosins, rosin esters,
hydrogenated rosins, hydrogenated rosin esters, polymerized rosins,
polymerized rosin esters, modified rosins, rosin-modified phenolic
resins, alkyl phenolic resins, aliphatic petroleum resins, aromatic
petroleum resins, hydrogenated petroleum resins, modified petroleum
resins, alicyclic petroleum resins, coumar one petroleum resins,
indene petroleum resins, olefin polymers (e.g., methylpentene
copolymers), cycloolefin polymers (e.g., norbornene copolymers,
dicyclopentadiene copolymers, tetracyclododecene copolymers) and
the like.
[0121] Among others, preferred are polystyrene resins, terpene
resins, rosins, petroleum resins, hydrogenated rosins, polymerized
rosins, olefin polymers, and cycloolefin polymers, more preferably
polystyrene resins, terpene resins, rosins, olefin polymers, and
cycloolefin polymers, even more preferably polystyrene resins,
terpene resins, rosins, olefin polymers, polystyrene resins, and
cycloolefin polymers, especially preferably polystyrene resins,
terpene resins, rosins, cycloolefin polymers, and olefin polymers,
most preferably polystyrene resins or cycloolefin polymers.
[0122] Examples of cyclic olefin resins used for preparing
cycloolefin copolymers include norbornene polymers, monocyclic
olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic
hydrocarbon polymers, and hydrides of these polymers and the like.
Preferred examples include addition (co)polymerized cyclic olefin
resins containing at least one or more repeat units represented by
general formula (II) below, and those addition (co)polymerized
cyclic olefin resins further containing at least one or more repeat
units represented by general formula (I) as appropriate. Further,
other preferred examples include ring-opened (co)polymers
containing at least one cyclic repeat unit represented by general
formula (III).
##STR00001##
[0123] In the formulae above, m represents an integer of 0 to 4.
R.sup.1 to R.sup.6 each independently represent a hydrogen atom or
a hydrocarbon group containing 1 to 10 carbon atoms, and X.sup.1 to
X.sup.3 and Y.sup.1 to Y.sup.3 each independently represent a
hydrogen atom, a hydrocarbon group containing 1 to 10 carbon atoms,
a halogen atom, a hydrocarbon group containing 1 to 10 carbon atoms
substituted by a halogen atom, --(CH.sub.2)nCOOR.sup.11,
--(CH.sub.2)nOCOR.sup.12, --(CH.sub.2)nNCO, --(CH.sub.2)nNO.sub.2,
--(CH.sub.2)nCN, --(CH2) nCONR.sup.13R.sup.-4,
--(CH.sub.2)nNR.sup.13R.sup.14, --(CH.sub.2)nOZ, or --(CH.sub.2)nW,
or X.sup.1 and Y.sup.1, X.sup.2 and Y.sup.2, or X.sup.3 and Y.sup.3
are joined to form (--CO).sub.2O or (--CO).sub.2NR.sup.15 wherein
R.sup.11, R.sup.12, R.sup.13, R.sup.14 and R.sup.15 each
independently represent a hydrogen atom or a hydrocarbon group
containing 1 to 20 carbon atoms, Z represents a hydrocarbon group
or a hydrocarbon group substituted by a halogen atom, and W
represents SiR.sup.16.sub.pD.sub.3-p (wherein R.sup.16 represents a
hydrocarbon group containing 1 to 10 carbon atoms, D represents a
halogen atom, --OCOR.sup.16 or --OR.sup.16, and p represents an
integer of 0 to 3). n represents an integer of 0 to 10.
[0124] Norbornene addition (co)polymers are disclosed in
JPA-H10-7732, JPA2002-504184, US2004/229157A1 or WO2004/070463A1 or
the like. They are obtained by addition polymerization of
norbornene polycyclic unsaturated compounds. Alternatively, they
are obtained by addition polymerization of a norbornene polycyclic
unsaturated compound with ethylene, propylene, butene; or a
conjugated diene such as butadiene or isoprene; or a non-conjugated
diene such as ethylidene norbornene. Such norbornene addition
(co)polymers are commercially available from Mitsui Chemicals, inc.
under the brand name APEL, including grades of different glass
transition temperatures (Tg) such as APL8008T (Tg 70.degree. C.) ,
APL6013T (Tg 125.degree. C.) or APL6015T (Tg 145.degree. C.).
Pellets are commercially available from Polyplastics Co., Ltd.
under the brand names TOPAS 8007, 5013, 6013, 6015 and the
like.
[0125] Another commercial product is Appear 3000 available from
Ferrania.
[0126] Norbornene polymer hydrides can be prepared by addition
polymerization or ring-opening metathesis polymerization of
polycyclic unsaturated compounds followed by hydrogenation as
disclosed in JPA-H1-240517, JPA-H7-196736, JPA-S60-26024,
JPA-S62-19801, JPA2003-1159767 or JPA2004-309979 or the like. In
the formulae above, R.sup.5 to R.sup.6 preferably represent a
hydrogen atom or --CH.sub.3, X.sup.3 and Y.sup.3 preferably
represent a hydrogen atom, and the other groups are appropriately
selected. Such norbornene resins are commercially available from
JSR Corporation under the brand name Arton G or Arton F, and also
from Zeon Corporation under the brand names ZEONOR ZF14 and ZF16,
and ZEONEX 250, 280 and 480R, and these products can be used.
[0127] The amount of the binder is preferably 30 to 80% by mass,
more preferably 40 to 60% by mass based on the total solids of the
adhesive composition.
[0128] The binder may be used alone or as a combination of two or
more.
<<Polymerizable Monomer>>
[0129] In the present invention, any polymerizable monomers can be
used in the adhesive composition (therefore, the adhesive layer).
The polymerizable monomer here contains a polymerizable group. The
polymerizable group is a group that can be polymerized typically by
irradiation with active rays or radiation or by the action of free
radicals or an acid.
[0130] It should be noted that the polymerizable monomer is a
compound distinguished from the binder described above. The
polymerizable monomer is typically a low molecular weight compound,
preferably a low molecular weight compound having a molecular
weight of 2000 or less, more preferably a low molecular weight
compound having a molecular weight of 1500 or less, even more
preferably a low molecular weight compound having a molecular
weight of 900 or less. Typically, the low molecular weight compound
has a molecular weight of 100 or more.
[0131] Preferably, the polymerizable group is, for example, a
functional group capable of participating in an addition
polymerization reaction, and such functional groups capable of
participating in an addition polymerization reaction include
ethylenically unsaturated bond-containing groups, amino, epoxy and
the like. The polymerizable group may also be a functional group
capable of generating free radicals when photoirradiated, and such
polymerizable groups include, for example, thiol, halogens and the
like. Among others, preferred polymerizable groups are
ethylenically unsaturated bond-containing groups. Ethylenically
unsaturated bond-containing groups preferably include styryl,
(meth)acryloyl, and allyl.
[0132] Reactive compounds containing a polymerizable group
specifically include (B1) radically polymerizable compounds and
(B2) ionically polymerizable compounds. Radically polymerizable
compounds include (B11) (meth)acrylamide compounds containing 3 to
35 carbon atoms, (B12) (meth)acrylate compounds containing 4 to 35
carbon atoms, (B13) aromatic vinyl compounds containing 6 to 35
carbon atoms, (B14) vinyl ether compounds containing 3 to 20 carbon
atoms, and (B15) other radically polymerizable compounds and the
like. The radically polymerizable compounds (B1) may be used alone
or as a combination of two or more of them.
[0133] Further, polymerization inhibitors such as hydroquinones,
methyl ether hydroquinones and the like may also be used, as
appropriate.
[0134] (Meth)acrylamide compounds containing 3 to 35 carbon atoms
(B11) include, for example, (meth)acrylamide,
N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide,
N-propyl(meth)acrylamide, N-n-butyl(meth)acrylamide,
N-tert-butyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide,
N-isopropyl(meth)acrylamide, N-methylol(meth)acrylamide,
N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide and
(meth)acryloylmorpholine.
[0135] (Meth)acrylate compounds containing 4 to 35 carbon atoms
(B12) include, for example, the monofunctional to hexafunctional
(meth)acrylates mentioned below.
[0136] Monofunctional (meth)acrylates include ethyl(meth)acrylate,
hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate,
tert-octyl(meth)acrylate, isoamyl(meth)acrylate,
decyl(meth)acrylate, isodecyl(meth)acrylate, stearyl(meth)acrylate,
isostearyl(meth)acrylate, cyclohexyl(meth)acrylate,
4-n-butylcyclohexl(meth)acrylate, bornyl(meth)acrylate,
isobornyl(meth)acrylate, benzyl(meth)acrylate, 2-ethylhexyl
diglycol(meth)acrylate, butoxyethyl(meth)acrylate,
2-chloroethyl(meth)acrylate, 4-bromobutyl(meth)acrylate,
cyanoethyl(meth)acrylate, benzyl(meth)acrylate,
butoxymethyl(meth)acrylate, methoxypropylene monoacrylate,
3-methoxybutyl(meth)acrylate, alkoxymethyl(meth)acrylate,
2-ethylhexyl carbitol(meth)acrylate, alkoxyethyl(meth)acrylate,
2-(2-methoxyethoxy)ethyl(meth)acrylate,
2-(2-butoxyethoxy)ethyl(meth)acrylate,
2,2,2-tetrafluoroethyl(meth)acrylate,
1H,1H,2H,2H-perfluorodecyl(meth)acrylate,
4-butylphenyl(meth)acrylate, phenyl(meth)acrylate,
2,4,5-tetramethylphenyl(meth)acrylate,
4-chlorophenyl(meth)acrylate, phenoxymethyl(meth)acrylate,
phenoxyethyl(meth)acrylate, glycidyl(meth)acrylate,
glycidyloxybutyl(meth)acrylate, glycidyloxyethyl(meth)acrylate,
glycidyloxypropyl(meth)acrylate, diethylene glycol monovinyl ether
monoacrylate, tetrahydrofurfuryl(meth)acrylate,
hydroxyalkyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate,
3-hydroxypropyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate,
2-hydroxybutyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate,
dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate,
dimethylaminopropyl(meth)acrylate,
diethylaminopropyl(meth)acrylate,
trimethoxysilylpropyl(meth)acrylate,
trimethoxysilylpropyl(meth)acrylate,
trimethylsilylpropyl(meth)acrylate, poly(ethylene oxide)monomethyl
ether(meth)acrylate, oligo(ethylene oxide)monomethyl
ether(meth)acrylate, poly(ethylene oxide)(meth)acrylate,
oligo(ethylene oxide)(meth)acrylate, oligo(ethylene oxide)monoalkyl
ether(meth)acrylate, poly(ethylene oxide)monoalkyl
ether(meth)acrylate, dipropylene glycol(meth)acrylate,
poly(propylene oxide)monoalkyl ether(meth)acrylate, oligo(propylene
oxide)monoalkyl ether(meth)acrylate, 2-methacryloyloxyethylsuccinic
acid, 2-methacryloyloxyhexahydrophthalic acid,
2-methacryloyloxyethyl-2-hydroxypropyl phthalate, butoxydiethylene
glycol(meth)acrylate, trifluoroethyl(meth)acrylate,
perfluorooctylethyl(meth)acrylate,
2-hydroxy-3-phenoxypropyl(meth)acrylate, EO-modified
phenol(meth)acrylate, EO-modified cresol(meth)acrylate, EO-modified
nonylphenol(meth)acrylate, PO-modified nonylphenol(meth)acrylate
and EO-modified 2-ethylhexyl(meth)acrylate and the like. As used
hereinbefore and hereinafter, EO means ethylene oxide, and PO means
propylene oxide.
[0137] Bifunctional(meth)acrylates include 1,4-butane
di(meth)acrylate, 1,6-hexane diacrylate, polypropylene diacrylate,
1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate,
neopentyl diacrylate, neopentyl glycol di(meth)acrylate,
2,4-dimethyl-1,5-pentanediol di(meth)acrylate,
butylethylpropanediol(meth)acrylate, ethoxylated
cyclohexanemethanol di(meth)acrylate, polyethylene glycol
di(meth)acrylate, oligoethylene glycol di(meth)acrylate, ethylene
glycol di(meth)acrylate, 2-ethyl-2-butyl butanediol
di(meth)acrylate, neopentyl glycol hydroxypivalate
di(meth)acrylate, EO-modified bisphenol A di(meth)acrylate,
bisphenol F polyethoxy di(meth)acrylate, polypropylene glycol
di(meth)acrylate, oligopropylene glycol di(meth)acrylate,
1,4-butanediol di(meth)acrylate, 2-ethyl-2-butyl propanediol
di(meth)acrylate, 1,9-nonane di(meth)acrylate, propoxylated
ethoxylated bisphenol A di(meth)acrylate and tricyclodecane
di(meth)acrylate and the like.
[0138] Trifunctional (meth)acrylates include trimethylolpropane
tri(meth)acrylate, trimethylolethane tri(meth)acrylate, alkylene
oxide modified tri(meth)acrylate of trimethylolpropane,
pentaerythritol tri(meth)acrylate, dipentaerythritol
tri(meth)acrylate, trimethylolpropane tri((meth)acryloyloxypropyl)
ether, alkylene oxide modified isocyanurate tri(meth)acrylate,
dipentaerythritol propionate tri(meth)acrylate,
tri((meth)acryloyloxyethyl) isocyanurate, hydroxypivalaldehyde
modified dimethylolpropane tri(meth)acrylate, sorbitol
tri(meth)acrylate, propoxylated trimethylolpropane
tri(meth)acrylate and ethoxylated glycerol triacrylate and the
like.
[0139] Tetrafunctional (meth)acrylates include pentaerythritol
tetra(meth)acrylate, sorbitol tetra(meth)acrylate,
ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol
propionate tetra(meth)acrylate and ethoxylated pentaerythritol
tetra(meth)acrylate and the like.
[0140] Pentafunctional (meth)acrylates include sorbitol
penta(meth)acrylate and dipentaerythritol penta(meth)acrylate.
[0141] Hexafunctional (meth)acrylates include dipentaerythritol
hexa(meth)acrylate, sorbitol hexa(meth)acrylate, alkylene oxide
modified hexa(meth)acrylate of phosphazene and caprolactone
modified dipentaerythritol hexa(meth)acrylate and the like.
[0142] Aromatic vinyl compounds containing 6 to 35 carbon atoms
(B13) include vinylthiophene, vinylfuran, vinylpyridine, styrene,
methylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene,
chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene,
dichlorostyrene, bromostyrene, methyl vinylbenzoate ester,
3-methylstyrene, 4-methylstyrene, 3-ethylstyrene, 4-ethylstyrene,
3-propylstyrene, 4-propylstyrene, 3-butylstyrene, 4-butylstyrene,
3-hexylstyrene, 4-hexylstyrene, 3-octylstyrene, 4-octylstyrene,
3-(2-ethylhexyl)styrene, 4-(2-ethylhexyl)styrene, allylstyrene,
isopropenylstyrene, butenylstyrene, octenylstyrene,
4-tert-butoxycarbonylstyrene, 4-methoxystyrene and
4-tert-butoxystyrene and the like.
[0143] Vinyl ether compounds containing 3 to 35 carbon atoms (B14)
include, for example, the following monofunctional or
polyfunctional vinyl ethers.
[0144] Monofunctional vinyl ethers include, for example, methyl
vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl
ether, tert-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl
vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether,
cyclohexylmethyl vinyl ether, 4-methylcyclohexylmethyl vinyl ether,
benzyl vinyl ether, dicyclopentenyl vinyl ether,
2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether,
ethoxyethyl vinyl ether, butoxyethyl vinyl ether,
methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether,
methoxypolyethylene glycol vinyl ether, tetrahydrofurfuryl vinyl
ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether,
4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexylmethyl vinyl
ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl
ether, chloroethyl vinyl ether, chlorobutyl vinyl ether,
chloroethoxyethyl vinyl ether, phenylethyl vinyl ether and
phenoxypolyethylene glycol vinyl ether.
[0145] Polyfunctional vinyl ethers include, for example, divinyl
ethers such as ethylene glycol divinyl ether, diethylene glycol
divinyl ether, polyethylene glycol divinyl ether, propylene glycol
divinyl ether, butylene glycol divinyl ether, hexanediol divinyl
ether, bisphenol A alkylene oxide divinyl ether, bisphenol F
alkylene oxide divinyl ether and the like; trimethylolethane
trivinyl ether, trimethylolpropane trivinyl ether,
ditrimethylolpropane tetravinyl ether, glycerol trivinyl ether,
pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl
ether, dipentaerythritol hexavinyl ether, ethylene oxide modified
trimethylolpropane trivinyl ether, propylene oxide modified
trimethylolpropane trivinyl ether, ethylene oxide modified
ditrimethylolpropane tetravinyl ether, propylene oxide modified
ditrimethylolpropane tetravinyl ether, ethylene oxide modified
pentaerythritol tetravinyl ether, propylene oxide modified
pentaerythritol tetravinyl ether, ethylene oxide modified
dipentaerythritol hexavinyl ether and propylene oxide modified
dipentaerythritol hexavinyl ether.
[0146] Other radically polymerizable compounds (B15) include vinyl
ester compounds (vinyl acetate, vinyl propionate and vinyl
versatate and the like), allyl ester compounds (allyl acetate and
the like), halogen-containing monomers (vinylidene chloride and
vinyl chloride and the like) and olefin compounds (ethylene and
propylene and the like) and the like.
[0147] Among them, (meth)acrylamide compounds (B11) and
(meth)acrylate compounds (B12) are preferred, especially preferably
(meth)acrylate compounds (B12) because of the rate of
polymerization.
[0148] Ionically polymerizable compounds (B2) include (B21) epoxy
compounds containing 3 to 20 carbon atoms and (B22) oxetane
compounds containing 4 to 20 carbon atoms and the like.
[0149] Epoxy compounds containing 3 to 20 carbon atoms (B21)
include, for example, the following monofunctional or
polyfunctional epoxy compounds.
[0150] Monofunctional epoxy compounds include, for example, phenyl
glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl
ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether,
1,2-butylene oxide, 1,3-butadiene monoxide, 1,2-epoxydodecane,
epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide,
3-methacryloyloxymethylcyclohexene oxide,
3-acryloyloxymethylcyclohexene oxide and 3-vinylcyclohexene
oxide.
[0151] Polyfunctional epoxy compounds include, for example,
bisphenol A diglycidyl ether, bisphenol F diglycidyl ether,
bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl
ether, brominated bisphenol F diglycidyl ether, brominated
bisphenol S diglycidyl ether, epoxy novolac resins, hydrogenated
bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl
ether, hydrogenated bisphenol S diglycidyl ether,
3,4-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate,
2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane,
bis(3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene oxide,
4-vinylepoxycyclohexane, bis(3,4-epoxy-6-methylcyclohexylmethyl)
adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcycloh
exane carboxylate, methylenebis(3,4-epoxycyclohexane),
dicyclopentadiene diepoxide, ethylene glycol
di(3,4-epoxycyclohexylmethyl) ether,
ethylenebis(3,4-epoxycyclohexane carboxylate), dioctyl
epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate,
1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether,
glycerol triglycidyl ether, trimethylolpropane triglycidyl ether,
polyethylene glycol diglycidyl ether, polypropylene glycol
diglycidyl ethers, 1,1,3-tetradecadiene dioxide, limonene dioxide,
1,2,7,8-diepoxyoctane and 1,2,5,6-diepoxycyclooctane.
[0152] Among these epoxy compounds, aromatic epoxides and alicyclic
epoxides are preferred, especially preferably alicyclic epoxides
because of the high rate of polymerization.
[0153] Oxetane compounds containing 4 to 20 carbon atoms (B22)
include compounds containing 1 to 6 oxetane rings and the like.
[0154] Compounds containing one oxetane ring include, for example,
3-ethyl-3-hydroxymethyloxetane,
3-(meth)allyloxymethyl-3-ethyloxetane,
(3-ethyl-3-oxetanylmethoxy)methylbenzene,
4-fluoro-[1-(3-ethyl-3-oxetanylmethoxy)methyl]benzene,
4-methoxy-[1-(3-ethyl-3-oxetanylmethoxy)methyl]benzene,
[1-(3-ethyl-3-oxetanylmethoxy)ethyl]phenyl ether,
isobutoxymethyl(3-ethyl-3-oxetanylmethyl)ether,
isobornyloxyethyl(3-ethyl-3-oxetanylmethyl)ether,
isobornyl(3-ethyl-3-oxetanylmethyl)ether,
2-ethylhexyl(3-ethyl-3-oxetanylmethyl) ether, ethyldiethylene
glycol(3-ethyl-3-oxetanylmethyl)ether,
dicyclopentadiene(3-ethyl-3-oxetanylmethyl)ether,
dicyclopentenyloxyethyl(3-ethyl-3-oxetanylmethyl)ether,
dicyclopentenyl(3-ethyl-3-oxetanylmethyl)ether,
tetrahydrofurfuryl(3-ethyl-3-oxetanylmethyl)ether,
tetrabromophenyl(3-ethyl-3-oxetanylmethyl)ether,
2-tetrabromophenoxyethyl(3-ethyl-3-oxetanylmethyl)ether,
tribromophenyl(3-ethyl-3-oxetanylmethyl)ether,
2-tribromophenoxyethyl(3-ethyl-3-oxetanylmethyl)ether,
2-hydroxyethyl(3-ethyl-3-oxetanylmethyl)ether,
2-hydroxypropyl(3-ethyl-3-oxetanylmethyl)ether,
butoxyethyl(3-ethyl-3-oxetanylmethyl)ether,
pentachlorophenyl(3-ethyl-3-oxetanylmethyl)ether,
pentabromophenyl(3-ethyl-3-oxetanylmethyl)ether and
bornyl(3-ethyl-3-oxetanylmethyl)ether.
[0155] Compounds containing 2 to 6 oxetane rings include, for
example, 3,7-bis(3-oxetanyl)-5-oxanonane,
3,3'-(1,3-(2-methylenyl)propanediylbis(oxymethylene))bis(3-ethyloxetane),
1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene,
1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane,
1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol
bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl
bis(3-ethyl-3-oxetanylmethyl)ether, triethylene glycol
bis(3-ethyl-3-oxetanylmethyl)ether, tetraethylene glycol
bis(3-ethyl-3-oxetanylmethyl)ether,
tricyclodecanediyldimethylene(3-ethyl-3-oxetanylmethyl)ether,
trimethylolpropane tris(3-ethyl-3-oxetanylmethyl)ether,
1,4-bis(3-ethyl-3-oxetanylmethoxy)butane,
1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, pentaerythritol
tris(3-ethyl-3-oxetanylmethyl)ether,
pentaerythritoltetrakis(3-ethyl-3-oxetanylmethyl)ether,
polyethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether,
dipentaerythritol hexakis(3-ethyl-3-oxetanylmethyl)ether,
dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl)ether,
dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl)ether,
caprolactone modified dipentaerythritol
hexakis(3-ethyl-3-oxetanylmethyl)ether, caprolactone modified
dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl)ether,
ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl)ether,
EO-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether,
PO-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether,
EO-modified hydrogenated bisphenol A
bis(3-ethyl-3-oxetanylmethyl)ether, PO-modified hydrogenated
bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether and EO-modified
bisphenol F(3-ethyl-3-oxetanylmethyl)ether.
[0156] The amount of the polymerizable monomer contained is
preferably 5 to 75% by mass, more preferably 10 to 70% by mass,
even more preferably 10 to 60% by mass based on the total solids of
the adhesive layer to achieve good bond strength and
releasability.
[0157] Further, the ratio between the contents of the polymerizable
monomer and the binder (mass ratio) is preferably 90/10 to 10/90,
more preferably 20/80 to 80/20.
[0158] The polymerizable monomer may be used alone or as a
combination of two or more.
<<Solvent>>
[0159] Any known solvents that can form the adhesive layer can be
used without limitation, including N-methyl-2-pyrrolidone,
2-butanone, methyl amyl ketone, limonene, PGMEA (1-methoxy-2-propyl
acetate) and the like, preferably N-methyl-2-pyrrolidone,
2-butanone, methyl amyl ketone, limonene, or PGMEA
(1-methoxy-2-propyl acetate). The solvents are preferably used in
such an amount that the solids content of the adhesive composition
is 5 to 40% by mass.
[0160] The solvents may be used alone or as a combination of two or
more of them. <<Photoinitiator>>
[0161] The adhesive composition (therefore, the adhesive layer)
preferably contains a photoinitiator, i.e., a compound capable of
generating free radicals or an acid when irradiated with active
rays or radiation.
[0162] The presence of a photoinitiator allows the adhesive
composition to be cured by free radicals or an acid when the
adhesive layer is photoirradiated, whereby adhesiveness in the
photo irradiated region decreases. If the sur face of the adhesive
layer is irradiated through a photomask, for example, it would have
the advantage that regions of different bond strengths can be
easily prepared according to the pattern of the photomask.
[0163] Compounds capable of generating free radicals or an acid
when irradiated with active rays or radiation that can be used
include, for example, those known as photoinitiators described
below.
[0164] The photoinitiator is not specifically limited so far as it
has the ability to initiate a polymerization reaction (crosslinking
reaction) in a high molecular weight compound containing a
polymerizable group serving as the binder or in a reactive compound
containing a polymerizable group serving as the polymerizable
monomer, and it can be appropriately selected from known
photoinitiators. For example, it is preferably sensitive to
radiations from UV to visible regions. Further, it may be an
activator capable of producing a reaction with a photoexcited
sensitizer to generate active free radicals or an initiator capable
of initiating cationic polymerization by generating an acid
depending on the type of the monomer.
[0165] Further, the photoinitiator preferably contains at least one
compound having a molar absorption coefficient of at least about 50
in the range of about 300 nm to 800 nm (preferably 330 nm to 500
nm).
[0166] Any of those known compounds can be used as the
photoinitiator without limitation, including, for example,
halogenated hydrocarbon derivatives (e.g., those containing a
triazine skeleton, those containing an oxadiazole skeleton, those
containing a trihalomethyl group, and the like), acyl phosphine
compounds such as acyl phosphine oxide, hexaaryl biimidazole, oxime
compounds such as oxime derivatives, organic peroxides, thio
compounds, ketone compounds, aromatic onium salts, ketoxime ethers,
aminoacetophenone compounds, hydroxyacetophenone, azo compounds,
azide compounds, metallocene compounds, organoboron compounds,
iron-arene complexes and the like.
[0167] The halogenated hydrocarbon compounds containing a triazine
skeleton include, for example, the compounds described in Bull.
Chem. Soc. Japan, 42, 2924 (1969) by Wakabayashi et al.; the
compounds described in GB 1388492(A); the compounds described in
JP-A-S53-133428; the compounds described in DE 3337024 A1; the
compounds described in J. Org. Chem., 29, 1527 (1964) by F. C.
Schaefer et al.; the compounds described in JP-A-S62-58241; the
compounds described in JP-A-H5-281728; the compounds described in
JP-A-H5-34920; the compounds described in U.S. Pat. No. 4,212,976
and the like.
[0168] The compounds described in U.S. Pat. No. 4,212,976 include,
for example, compounds containing an oxadiazole skeleton (e.g.,
2-trichloromethyl-5-phenyl-1,3,4-oxadiazole,
2-trichloromethyl-5-(4-chlorophenyl)-1,3,4-oxadiazole,
2-trichloromethyl-5-(1-naphthyl)-1,3,4-oxadiazole,
2-trichloromethyl-5-(2-naphthyl)-1,3,4-oxadiazole,
2-tribromomethyl-5-phenyl-1,3,4-oxadiazole,
2-tribromomethyl-5-(2-naphthyl)-1,3,4-oxadiazole,
2-trichloromethyl-5-styryl-1,3,4-oxadiazole,
2-trichloromethyl-5-(4-chlorostyryl)-1,3,4-oxadiazole,
2-trichloromethyl-5-(4-methoxystyryl)-1,3,4-oxadiazole,
2-trichloromethyl-5-(1-naphthyl)-1,3,4-oxadiazole,
2-trichloromethyl-5-(4-n-butoxystyryl)-1,3,4-oxadiazole,
2-tribromomethyl-5-styryl-1,3,4-oxadiazole, etc.), and the
like.
[0169] Photoinitiators other than those described above include
acridine derivatives (e.g., 9-phenylacridine,
1,7-bis(9,9'-acridinyl)heptane, etc.), N-phenylglycine and the
like, polyhalogen compounds (e.g., carbon tetrabromide, phenyl
tribromomethyl sulfone, phenyl trichloromethyl ketone, etc.),
coumarins (e.g., 3-(2-benzofuranoyl)-7-diethylaminocoumarin,
3-(2-benzofuroyl)-7-(1-pyrrolidinyl)coumarin,
3-benzoyl-7-diethylaminocoumarin,
3-(2-methoxybenzoyl)-7-diethylaminocoumarin,
3-(4-dimethylaminobenzoyl)-7-diethylaminocoumarin,
3,3'-carbonylbis(5,7-di-n-propoxycoumarin),
3,3'-carbonylbis(7-diethylaminocoumarin),
3-benzoyl-7-methoxycoumarin, 3-(2-furoyl)-7-diethylaminocoumarin,
3-(4-diethylaminocinnamoyl)-7-diethylaminocoumarin,
7-methoxy-3-(3-pyridylcarbonyl)coumarin,
3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, the
coumarin compounds described in JP-A-H5-19475, JP-A-H7-271028,
JP-A2002-363206, JP-A2002-363207, JP-A2002-363208, JP-A2002-363209
and the like, etc.), acyl phosphine oxides (e.g.,
bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide,
bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphenylpho sphine
oxide, Lucirin TPO, etc.), metallocenes (e.g.,
bis(.eta.5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)ph-
enyl) titanium, (.eta.5-cyclopentadienyl) (.eta.6-cumenyl)iron (1+)
hexafluorophosphate (1-), etc.), and the compounds described in
JP-A-S53-133428, JP-B-S57-1819, JP-B-S57-6096 and U.S. Pat. No.
3,615,455, and the like.
[0170] The ketone compounds include, for example, benzophenone,
2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone,
4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone,
4-bromobenzophenone, 2-carboxybenzophenone,
2-ethoxycarbonylbenzophenone, benzophenonetetracarboxylic acid or
its tetramethyl ester, 4,4'-bis(dialkylamino)benzophenones (e.g.,
4,4'-bis(dimethylamino)benzophenone,
4,4'-bis(dicyclohexylamino)benzophenone,
4,4'-bis(diethylamino)benzophenone,
4,4'-bis(dihydroxyethylamino)benzophenone,
4-methoxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone,
and 4-dimethylaminobenzophenone), 4-dimethylaminoacetophenone,
benzil, anthraquinone, 2-tert-butylanthraquinone,
2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone,
2-chlorothioxanthone, 2,4-diethylthioxanthone, fluorenone,
2-benzyldimethylamino-1-(4-morpholinophenyl)-1-butanone,
2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone,
2-hydroxy-2-methyl-[4-(1-methylvinyl)phenyl]propanol oligomers,
benzoin, benzoin ethers (e.g., benzoin methyl ether, benzoin ethyl
ether, benzoin propyl ether, benzoin isopropyl ether, benzoin
phenyl ether, and benzil dimethyl ketal), acridone, chloroacridone,
N-methylacridone, N-butylacridone, N-butylchloroacridone, etc.
[0171] Other photoinitiators that can be suitably used include
hydroxyacetophenone compounds, aminoacetophenone compounds, and
acylphosphine compounds. More specifically, the aminoacetophenone
initiators described in JP-A-H10-291969 and the acylphosphine oxide
initiators described in Japanese Patent No. 4225898 can also be
used, for example.
[0172] Hydroxyacetophenone initiators that can be used include
IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959 and
IRGACURE-127 (all brand names from BASF). Aminoacetophenone
initiators that can be used include commercially available products
IRGACURE-907, IRGACURE-369, and IRGACURE-379 (all brand names from
BASF). Other aminoacetophenone initiators that can be used include
the compounds having an absorption wavelength matched to a source
of long wave radiation such as 365 nm or 405 nm described in
JP-A2009-191179. Acylphosphine initiators that can be used include
commercially available products IRGACURE-819 and DAROCUR-TPO (both
brand names from BASF).
[0173] Photoinitiators more preferably include oxime compounds.
Specific examples of oxime initiators that can be used include the
compounds described in JP-A2001-233842, the compounds described in
JP-A2000-80068, and the compounds described in JP-A2006-342166.
[0174] Oxime compounds such as oxime derivatives suitably used as
photoinitiators in the present invention include, for example,
3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one,
3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one,
2-acetoxyimino-1-phenylpropan-1-one,
2-benzoyloxyimino-1-phenylpropan-1-one,
3-(4-toluenesulfonyloxy)iminobutan-2-one, and
2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.
[0175] Oxime ester compounds include the compounds described in J.
C. S. Perkin II (1979) pp. 1653-1660, J. C. S. Perkin II (1979) pp.
156-162, Journal of Photopolymer Science and Technology (1995) pp.
202-232 and JP-A2000-66385; the compounds described in
JP-A2000-80068, JP-A2004-534797, and JP-A2006-342166 and the
like.
[0176] Commercially available products such as IRGACURE-OXE01 (from
BASF) and IRGACURE-OXE02 (from BASF) can also be suitably used.
[0177] Oxime ester compounds other than those described above that
may be used include the compounds containing an oxime moiety
substituted on the nitrogen atom of a carbazole described in
JP-A2009-519904; the compounds containing a hetero substituent on
the benzophenone moiety described in U.S. Pat. No. 7,626,957; the
compounds containing a nitro group on the dye moiety described in
JP-A2010-15025 and U.S. Pat. Application Publication No.
2009/292039; the ketoxime compounds described in WO2009/131189; the
compounds containing a triazine skeleton and an oxime skeleton in
the same molecule described in U.S. Pat. No. 7,556,910; the
compounds having a maximum absorption at 405 nm and also having
good sensitivity to g-line sources described in JP-A2009-221114;
and the like.
[0178] Preferably, the cyclic oxime compounds described in
JP-A2007-231000 and JP-A2007-322744 can also be suitably used.
Among cyclic oxime compounds, the cyclic oxime compounds annulated
with a carbazole dye described in JP-A2010-32985 and
JP-A2010-185072 are especially preferred because of high
absorptivity leading to high sensitivity.
[0179] Further, the oxime compounds containing an unsaturated bond
at a specific site described in JP-A2009-242469 can also be
suitably used because they can regenerate active free radicals from
polymerization-inactive free radicals to achieve high
sensitivity.
[0180] Most preferred are the oxime compounds containing a specific
substituent shown in JP-A2007-269779 and the oxime compounds
containing a thioaryl group shown in JP-A2009-191061.
[0181] The molar absorption coefficient of a compound can be
determined by known methods, and specifically, it is preferably
determined at a concentration of 0.01 g/L in ethyl acetate as a
solvent by using an ultraviolet-visible spectrophotometer (Carry-5
spectrophotometer from Varian), for example.
[0182] The photoinitiators used in the present invention may be
used as a combination of two or more of them, if desired.
[0183] The amount of the photoinitiators contained in the adhesive
composition used in the present invention is preferably 0.01 to 50%
by mass, more preferably 0.1 to 20% by mass, most preferably 0.5 to
10% by mass based on the total solids of the adhesive
composition.
<<Thermal Polymerization Initiator>>
[0184] Preferably, the adhesive composition (therefore, the
adhesive layer) of the present invention also contains a thermal
polymerization initiator, i.e., a compound capable of generating
free radicals or an acid when heated.
[0185] Especially when it comprises a high molecular weight
compound containing a polymerizable group as the binder or the
polymerizable monomer, it preferably contains a thermal
polymerization initiator.
[0186] The presence of a thermal polymerization initiator has the
advantage that a more heat resistant and chemical resistant bond
can be formed by heating the adhesive layer at or higher than the
decomposition temperature of the thermal polymerization initiator
to cure it after the adhesive layer and the release layer have been
bonded.
[0187] The thermal polymerization initiator may be used alone or as
a combination of two or more.
<<<Compounds Capable of Generating Free Radicals When
Heated>>>
[0188] Compounds capable of generating free radicals when heated
(hereinafter also simply referred to as "thermal free radical
generator") that can be used include known thermal free radical
generators.
[0189] The thermal free radical generator is a compound capable of
generating free radicals by thermal energy to initiate or promote a
polymerization reaction of a high molecular weight compound
containing a polymerizable group and a polymerizable monomer. If an
adhesive layer formed by using an adhesive composition containing a
thermal free radical generator is irradiated with heat and then a
member to be processed and an adhesive support are temporarily
bonded, a crosslinking reaction proceeds by heat in a reactive
compound containing a crosslinkable group, whereby the adhesiveness
(i.e., stickiness and tackiness) of the adhesive layer can be
decreased in advance as described later.
[0190] If a member to be processed and an adhesive support are
temporarily bonded and then the adhesive layer in the adhesive
support is irradiated with heat, on the other hand, a crosslinking
reaction proceeds by heat in a reactive compound containing a
crosslinkable group, whereby the adhesive layer is strengthened
enough to prevent the adhesive layer from cohesive failure that
would be likely to occur during a mechanical or chemical process of
the member to be processed. Thus, the adhesiveness of the adhesive
layer can be improved.
[0191] Preferred thermal free radical generators include the
compounds capable of generating an acid or free radicals when
irradiated with active rays or radiation described above, among
which compounds having a thermal decomposition point in the range
of 130.degree. C. to 250.degree. C., preferably 150.degree. C. to
220.degree. C. can be preferably used.
[0192] Thermal free radical generators include aromatic ketones,
onium salt compounds, organic peroxides, thio compounds, hexaaryl
biimidazole compounds, ketoxime ester compounds, borate compounds,
azinium compounds, metallocene compounds, active ester compounds,
compounds containing a carbon-halogen bond, azo compounds and the
like. Among others, more preferred are organic peroxides or azo
compounds, especially preferably organic peroxides. Specifically,
the compounds described in paragraphs 0074 to 0118 of JPA2008-63554
are included.
[0193] Preferably, the adhesive layer comprises a binder, a
polymerizable monomer, and at least one of a photoinitiator and a
thermal polymerization initiator, more preferably a
photoinitiator.
[0194] When the adhesive composition (therefore, the adhesive
layer) according to the present invention further comprises a
radically polymerizable monomer especially in combination with a
photoinitiator or a thermal polymerization initiator, the adhesive
layer 11 can be an adhesive layer having adhesiveness that
decreases by irradiation with active rays or radiation or heat. In
this case, the adhesive layer can be specifically a layer having
adhesiveness before it is irradiated with active rays or radiation
or heat but the adhesiveness decreases or is lost in regions
irradiated with active rays or radiation or heat.
<<<Compounds Capable of Generating an Acid When
Heated>>>
[0195] Compounds capable of generating an acid when heated
(hereinafter also simply referred to as "thermal acid generators")
that can be used include known thermal acid generators.
[0196] Thermal acid generators preferably include compounds having
a thermal decomposition point in the range of 130.degree. C. to
250.degree. C., more preferably 150.degree. C. to 220.degree. C.
Thermal acid generators include, for example, compounds capable of
generating an acid with low nucleophilicity when heated, such as a
sulfonic acid, a carboxylic acid or a disulfonyl imide.
[0197] The acid generated from the thermal acid generators is
preferably a strong acid having a pKa of 2 or more such as a
sulfonic acid, an alkyl or aryl carboxylic acid substituted by an
electron-withdrawing group, a disulfonyl imide also substituted by
an electron-withdrawing group or the like. The electron-withdrawing
group includes a halogen atom such as fluorine atom, a haloalkyl
group such as trifluoromethyl, nitro, or cyano.
[0198] Thermal acid generators that can be applied include
photoinduced acid generators capable of generating an acid when
irradiated with active rays or radiation. For example, they include
onium salts such as sulfonium salts and iodonium salts;
N-hydroxyimide sulfonate compounds, oxime sulfonates, o-nitrobenzyl
sulfonate and the like.
[0199] Further, sulfonic acid esters substantially incapable of
generating an acid when irradiated with active rays or radiation
but capable of generating an acid when heated are also preferably
used in the present invention. A compound substantially incapable
of generating an acid when irradiated with active rays or radiation
can be identified by infrared (IR) absorption spectrometry or
nuclear magnetic resonance (NMR) spectrometry, which detects no
spectral change before and after the compound is exposed.
[0200] The sulfonic acid esters preferably have a molecular weight
of 230 to 1,000, more preferably 230 to 800. Sulfonic acid esters
that can be used in the present invention are commercially
available or synthesized by known methods. The sulfonic acid esters
can be synthesized by, for example, reacting a sulfonyl chloride or
a sulfonic anhydride with an appropriate polyhydric alcohol under
basic conditions.
[0201] The thermal acid generators may be used alone or as a
combination of two or more of them.
[0202] The amount of the thermal polymerization initiator contained
in the adhesive composition of the present invention is preferably
0.01 to 50% by mass, more preferably 0.1 to 20% by mass, most
preferably 0.5 to 10% by mass based on the total solids of the
adhesive composition in order that the adhesiveness of the adhesive
layer can be reduced when it is irradiated with heat before a
member to be processed and an adhesive support are temporarily
bonded while the adhesiveness of the adhesive layer can be improved
when it is irradiated with heat after a member to be processed and
an adhesive support have been temporarily bonded.
<<Other Components>>
[0203] In addition to the components described above, the adhesive
composition (therefore, the adhesive layer) may further contain
various compounds depending on the purposes so far as the
advantages of the present invention are not adversely affected.
[0204] For example, sensitizing dyes, chain transfer agents,
polymerization inhibitors, and surfactants can be preferably
used.
[0205] Specific examples and preferred examples of surfactants that
may be contained in the adhesive composition (therefore, the
adhesive layer) are the same as the surfactants that may be
contained in the release layer composition described above.
[0206] In the present invention, the adhesive composition
preferably comprises a binder, a polymerizable monomer, a
photoinitiator and a thermal polymerization initiator.
[0207] The adhesive composition according to the present invention
may contain a rubber. As used herein, the "rubber" means to include
any natural rubbers and synthetic rubbers as well as elastomers.
Silicone rubbers may also be used.
[0208] Preferably, such a rubber is preferably contained at 4 to
20% by mass, more preferably 10 to 18% by mass, even more
preferably 14 to 17% by mass based on the total solids of the
adhesive composition.
[0209] More preferably, the rubber contains repeat monomer units of
ethylene and propylene. The amount of the ethylene monomer in the
rubber is preferably 40 to 70% by mass, more preferably 40 to 60%
by mass, even more preferably 40 to 50% by mass when the total
weight of the rubber is 100% by mass. The amount of the propylene
monomer in the rubber is preferably 35 to 65% by mass, more
preferably 35 to 55% by mass, even more preferably 35 to 45% by
mass when the total weight of the rubber is 100% by mass.
[0210] Still more preferably, the rubber further contains a small
amount of a non-conjugated diene (e.g., an ethylidene norbornene
monomer). The amount of the non-conjugated diene in the rubber is
preferably 1 to 10% by mass, more preferably 2 to 6% by mass, even
more preferably 2 to 3% by mass when the total weight of the rubber
is 100% by mass.
[0211] Especially preferred rubbers are ethylene-propylene-diene
monomers or ethylene-propylene terpolymers called EPDMs.
Ethylene-propylene terpolymers are commercially available under the
brand name BUNA (R) EP ((R) Represents a registered trademark) from
Lanxess.
[0212] A silicone rubber that can be used includes a material
available from WACKER, Burghausen under the brand name ELASTOSIL LR
3070 having a Shore A hardness of 50.
[0213] Further, the rubber may be used as a mixture with a
dissolved hydrocarbon resin. The hydrocarbon resin is preferably
contained at 65 to 95% by mass, more preferably 75 to 95% by mass,
even more preferably 80 to 90% by mass based on the total
solids.
[0214] The hydrocarbon resin to be mixed with the rubber can be
selected from the group consisting of terpene rosins, gum rosins,
wood rosins, and mixtures thereof. Preferred hydrocarbon resins are
commercially available under the brand name Eastotac from Eastman
Chemical Company.
[0215] The polysiloxane polymers described in paragraphs 0013 to
0015 of JPA2013-048215 or the silphenylene-containing compounds
described in paragraphs 0021 to 0027 of the same document may also
be used.
<Methods for Manufacturing Semiconductor Devices>
[0216] Next, adhesive supports using the temporary bonding
laminates for used in a manufacture of semiconductor devices
according to the present invention described above and methods for
manufacturing semiconductor devices (hereinafter also referred to
as "methods for manufacturing semiconductor devices according to
the present invention") are explained below.
[0217] The methods for manufacturing semiconductor devices
according to the present invention comprise: bonding a first
surface of a member to be processed and a substrate via a temporary
bonding laminate for used in a manufacture of semiconductor devices
according to the present invention; subjecting the member to be
processed to a heat treatment having a maximum attainable
temperature in the range of 180.degree. C. to 370.degree. C. to
give a processed member; and debonding the processed member from
the bonding layers; characterized in that the resin 1 has a
softening point higher than the maximum attainable temperature in
the heat treatment.
[0218] Each step is explained below.
[0219] The methods for manufacturing semiconductor devices
according to the present invention comprise performing a heat
treatment. The performing a heat treatment is not specifically
limited so far as it is a step comprising heating in a
manufacturing process of a semiconductor device, but preferably
e.g., a step comprising heating a thinned silicon substrate
supported on an adhesive support, more preferably a step comprising
a heat treatment during the formation of through-silicon vias.
[0220] The performing a heat treatment in the methods for
manufacturing semiconductor devices according to the present
invention is a step comprising a heat treatment having a maximum
attainable temperature in the range of 180.degree. C. to
370.degree. C., preferably a step comprising a heat treatment
having a maximum attainable temperature in the range of 180 to
250.degree. C. The softening point of the resin 1 is preferably
higher than the maximum attainable temperature in the heat
treatment by 20.degree. C. or more, more preferably 20 to
50.degree. C. When it is in such ranges, the advantages of the
present invention are achieved more effectively. The heat treatment
preferably comprises heating at the maximum attainable temperature
for 30 seconds to 30 minutes, more preferably heating at the
maximum attainable temperature for 1 minute to 10 minutes.
[0221] Further, the methods processes preferably also comprise
irradiating the adhesive layer of the temporary bonding laminate
with active rays or radiation or heat before the step of bonding
the first surface of the member to be processed and the substrate
via the temporary bonding laminate.
[0222] Further, the methods preferably also comprise removing the
temporary bonding laminate remaining on the processed member using
a stripping solvent after debonding the processed member from the
temporary bonding laminate.
[0223] In the methods for manufacturing semiconductor devices
according to the present invention, the stripping solvent
preferably comprises at least one of a hydrocarbon solvent and an
ether solvent.
[0224] In the embodiment described above, the methods may further
comprise removing the adhesive layer remaining on the processed
member using a stripping solvent after debonding the processed
member from the bonding layers. The stripping solvent here is
preferably selected from a hydrocarbon solvent and an ether solvent
or a combination thereof, more preferably selected from
cyclopentane, n-hexane, cyclohexane, n-heptane, limonene,
p-menthane, tetrahydrofuran (THF), 1,3-dioxolane and anisole or a
combination thereof, even more preferably comprises at least one of
tetrahydrofuran, 1,3-dioxolane and anisole.
[0225] The methods for manufacturing semiconductors according to
the present invention are explained in more detail below.
[0226] FIG. 3A, FIG. 3B and FIG. 3C are a schematic sectional view
illustrating how to temporarily bond an adhesive support and a
device wafer, a schematic sectional view showing the device wafer
temporarily bonded to the adhesive support, and a schematic
sectional view showing the device wafer temporarily bonded to the
adhesive support after it has been thinned, respectively.
[0227] In an embodiment of the present invention, an adhesive
support 100 comprising an adhesive layer 11 on a carrier substrate
12 is first provided, as shown in FIG. 3A. The carrier substrate 12
is not specifically limited to any materials, and includes, for
example, a silicon substrate, a glass substrate, a metal substrate
or the like, preferably a silicon substrate because it is less
likely to contaminate silicon substrates typically used as
substrates for semiconductor devices and it allows the use of an
electrostatic chuck commonly used in manufacturing methods of
semiconductor devices.
[0228] The thickness of the carrier substrate 12 is, for example,
in the range of 300 .mu.m to 5 mm, but not specifically
limited.
[0229] FIG. 4 is a schematic top view of an adhesive support
according to an embodiment of the present invention.
[0230] In the embodiment of the present invention, the adhesive
layer 11 in the adhesive support is formed of high adhesion regions
11A as dot regions, and low adhesion regions 11B as peripheral
regions surrounding the dot regions, as shown in FIG. 4. The low
adhesion regions 11B and the high adhesion regions 11A here are
distributed at an approximately equal distance over the entire
surface of the adhesive layer 11 to form a halftone pattern.
[0231] The low adhesion regions 11A and the high adhesion regions
11B are formed by pattern exposure to produce a halftone image on
the adhesive layer having adhesiveness that increases or decreases
by irradiation with active rays or radiation.
[0232] The pattern exposure to produce a halftone image is
preferably performed in such a manner that the dot regions of the
halftone pattern in the adhesive layer are the high adhesion
regions while the peripheral regions surrounding the dot regions
are the low adhesion regions. Preferably, each dot region has an
area of 0.0001 to 9 mm.sup.2, more preferably 0.1 to 4 mm.sup.2,
most preferably 0.01 to 2.25 mm.sup.2.
[0233] The pattern exposure to produce a halftone image may be mask
exposure or maskless exposure, but preferably mask exposure through
a photomask in which light-transmitting regions and light-shielding
regions form a halftone pattern, and in which case the area rate of
the light-shielding regions (i.e., the abundance of halftone dots
on the bonding surface) is preferably 1 to 20%, more preferably 1
to 10%, most preferably 1 to 5% in the mask because of adhesiveness
and releasability.
[0234] Further, the morphology (size, shape and the like) of the
light-shielding regions corresponding to the halftone dots in the
halftone pattern of the photomask can be selected at will, and each
light-shielding region may be in the shape of, for example, a
circle, square, rectangle, diamond, triangle or star or a
combination of two or more of them of any size.
[0235] As used herein, the "low adhesion regions" refer to regions
having lower adhesiveness as compared with "high adhesion regions",
and includes regions having no adhesiveness (i.e., "non-adhesive
regions"). Similarly, the "high adhesion regions" refer to regions
having higher adhesiveness as compared with "low adhesion
regions".
[0236] The adhesive layer 11 can be formed by applying (preferably
coating) an adhesive layer composition according to the present
invention in the form of a layer on the carrier substrate 12 using
a known technique such as spin coating, spray coating, roller
coating, flow coating, blade coating, dip coating or the like, and
then drying it. The adhesive layer may be baked after the adhesive
layer composition has been applied in the form of a layer. The
baking temperature is preferably 50 to 350.degree. C., more
preferably 80 to 120.degree. C. The baking time is preferably 10
seconds to 5 minutes.
[0237] The surface of the adhesive layer of the present invention
comprises two or more classes of regions having different bond
strengths.
[0238] As used herein, the bond strength refers to the bond
strength determined when a silicon wafer is bonded to the surface
of each region and subjected to a tensile test at 250 mm/min in a
direction perpendicular to the bonding surface.
[0239] The thickness of the adhesive layer 11 is, for example, in
the range of 1 to 500 .mu.m, more preferably 1 to 100 .mu.m, but
not specifically limited.
[0240] The release layer can be formed by applying (preferably
coating) a release layer composition in the form of a layer on a
member to be processed using a known technique such as spin
coating, spray coating, roller coating, flow coating, blade
coating, dip coating or the like, and then drying it. The release
layer may be baked after the release layer composition has been
applied in the form of a layer. Baking conditions preferably
include 50 to 350.degree. C., more preferably 60 to 300.degree. C.
The baking time is preferably 30 seconds to 20minutes. Baking may
be performed in two stages, in which case a first stage of baking
is preferably performed at a temperature lower than a second stage
of baking by about 30 to 100.degree. C.
[0241] The thickness of the release layer is, for example, in the
range of 1 to 500 .mu.m, more preferably 1 to 100 .mu.m, but not
specifically limited.
[0242] Next, temporarily bonding the adhesive support obtained as
described above and a device wafer, thinning the device wafer, and
debonding the device wafer from the adhesive support are explained
in detail below.
[0243] As shown in FIG. 3A, a device wafer 60 (processed member)
comprises multiple device chips 62 on a frontside 61a of a silicon
substrate 61. A release layer 71 is provided on the frontside of
the device wafer 60 having the device chips 62. A softening point
of the release layer 71 is 170.degree. C. or more.
[0244] The thickness of the silicon substrate 61 is, for example,
in the range of 200 to 1200 .mu.m.
[0245] Then, the surface 71 of the release layer 71 is applied on
the adhesive layer 11 of the adhesive support 100. Thus, the
surface of the release layer 71 and the adhesive layer 11 is bonded
to form a temporary bonding laminate 80 comprising the release
layer 71 and the adhesive layer 11, as shown in FIG. 3B.
[0246] Then, the bonded assembly of the adhesive support 100 and
the device wafer 60 may be heated (irradiated with heat) to
strengthen the adhesive layer, if desired. This allows the
adhesiveness of the adhesive support 100 to be higher because it
prevents the adhesive layer from cohesive failure that would be
likely to occur during a mechanical or chemical process of the
device wafer 60 as described later. Especially, the adhesive layer
preferably contains a thermal polymerization initiator because a
crosslinking reaction in a reactive compound containing a
crosslinkable group can be promoted by heat.
[0247] Then, the backside 61b of the silicon substrate 61 is
subjected to a mechanical or chemical process, specifically a
thinning process such as grinding or chemical mechanical polishing
(CMP), thereby reducing the thickness of the silicon substrate 61
(e.g., to a thickness of 1 to 200 .mu.m) to give a thinned device
wafer 60', as shown in FIG. 3C.
[0248] A further mechanical or chemical process after the thinning
process comprises forming through-holes (not shown) through the
silicon substrate from the backside 61b' of the thinned device
wafer and forming through-silicon vi as (not shown) in the
through-holes. The process of forming through-silicon vias
comprises performing a heat treatment having a maximum temperature
lower than the softening point of the release layer 71.
Specifically, the maximum attainable temperature in the heat
treatment is in the range of 130.degree. C. to 370.degree. C.,
preferably in the range of 180.degree. C. to 370.degree. C.
[0249] Then, the frontside 61a of the thinned device wafer 60' is
debonded from the adhesive layer 11 of the adhesive support
100.
[0250] The debonding method is not specifically limited, but
preferably comprises sliding the thinned device wafer 60' against
the adhesive support 100 or separating the thinned device wafer 60'
from the adhesive support 100. These methods allow the adhesive
layer 11 and the frontside 61a of the thinned device wafer 60' to
be readily released from the temporary bond.
[0251] After the thinned device wafer 60' is debonded from the
adhesive support 100, the thinned device wafer 60' is subjected
various known processes as appropriate to prepare a semiconductor
device comprising the thinned device wafer 60'.
[0252] In the present invention, the temporary bonding method is
not limited so far as a device wafer and a carrier substrate are
bonded via a temporary bonding laminate comprising a release layer
and an adhesive layer, and may comprise preparing a temporary
bonding laminate having a release layer on an adhesive layer in
advance and bonding a carrier substrate and a device wafer to the
adhesive layer and the release layer in this temporary bonding
laminate, respectively.
[0253] Further, the present invention also relates to a laminate
comprising a support such as a carrier substrate, a member to be
processed such as a device wafer, and a temporary bonding laminate
provided between the support and the member to be processed.
[0254] Next, a conventional embodiment is explained. FIG. 15 is a
schematic sectional view illustrating how an adhesive support and a
device wafer are released from a temporary bond according to a
prior art.
[0255] In the conventional embodiment, an adhesive support 100' and
a device wafer are temporarily bonded by the same procedure as
explained with reference to FIG. 3A and FIG. 3B except that the
adhesive support 100' comprises an adhesive layer 11' formed of a
conventional temporary bonding agent on a carrier substrate 12 as
shown in FIG. 13, then the silicon substrate in the device wafer is
thinned, and then a thinned device wafer 60' having the silicon
substrate 61 is separated from the adhesive support 100'.
[0256] When a conventional temporary bonding agent is used,
however, it is difficult to temporarily support a member to be
processed securely and readily and to readily release a processed
member from a temporary support without damaging the processed
member. If a conventional temporary bonding agent having high
adhesiveness is employed to sufficiently temporarily bond the
device wafer and the carrier substrate, for example, the temporary
bond between the device wafer and the carrier substrate tends to be
excessively strong. If a tape (e.g., a dicing tape) 70 is adhered
to the backside 61b' of the thinned device wafer 60' and the
thinned device wafer 60' is separated from the adhesive support 12
to resolve this excessively strong temporary bond, as shown in FIG.
15 for example, bumps 63 drop off from device chips 62 on which the
bumps 63 are provided or otherwise the device chips 62 are
disadvantageously likely to be broken.
[0257] If a conventional temporary bonding agent having low
adhesiveness is employed, however, the temporary bond between the
device wafer and the carrier substrate is too weak to securely
support the device wafer on the carrier substrate.
[0258] In contrast, an adhesive layer formed of an adhesive
composition of the present invention exhibits sufficient
adhesiveness and the temporary bond between the device wafer 60 and
the adhesive support 100 can be readily resolved because the
adhesive layer 11 comprises high adhesion regions and low adhesion
regions. Thus, the release layer in the temporary bonding laminate
of the present invention allows the device wafer 60 to be
temporarily bonded securely and readily and the thinned device
wafer 60' to be readily debonded without damaging the thinned
device wafer 60'.
[0259] The methods for manufacturing semiconductor devices
according to the present invention are not limited to the
embodiment described above, but modifications, improvements and the
like can be made as appropriate.
[0260] The shape of the halftone pattern in the adhesive layer is
not specifically limited, and an adhesive layer 21 may be formed to
have a halftone pattern comprising high adhesion regions 21A and
low adhesion regions 21B wherein the high adhesion regions 21A
extend outward from the center to form a radial pattern, as shown
in the schematic top view of FIG. 5, for example.
[0261] Alternatively, adhesive layers 22, 23, 24 may be formed to
have a pattern comprising high adhesion regions 22A, 23A, 24A and
low adhesion regions 22B, 23B, 24B wherein the high adhesion
regions 22A, 23A, 24A extend outward from the center to form a
radial pattern and have an area rate lower than the area rate of
the high adhesion regions 21A in the adhesive layer 21 (see FIG.
5), as shown in the schematic top views of FIGS. 6, 7, and 8.
[0262] Further, the size of each high adhesion region in the
halftone pattern is not specifically limited, and adhesive layers
25, 26, 27, 28, 29, 30 comprising high adhesion regions 25A, 26A,
27A, 28A, 29A, 30A and low adhesion regions 25B, 26B, 27B, 28B,
29B, 30B may be formed wherein the high adhesion regions 25A, 26A,
27A, 28A, 29A, 30A have a size changed from the size of the high
adhesion regions 11A in the adhesive layer 11 (see FIG. 4), as
shown in FIG. 9, 8, 9, 10, 11, 12.
[0263] Although an adhesive layer formed of an adhesive composition
of the present invention is provided on a carrier substrate to form
an adhesive support before it is temporarily bonded to a device
wafer in the embodiment described above, it may be first provided
on a release layer to form a temporary bonding laminate, in which
case the adhesive layer and the release layer in the temporary
bonding laminate are bonded to a carrier substrate and a device
wafer, respectively.
[0264] For example, the mask used for pattern exposure may be a
binary mask or a halftone mask.
[0265] Although exposure is performed through a mask, it may be
selective exposure using an electron beam or the like.
[0266] Further, the embodiment described above preferably further
comprises irradiating the adhesive layer of the temporary bonding
laminate with active rays or radiation or heat before bonding the
first surface of the member to be processed and the substrate via
the temporary bonding laminate.
[0267] Although the adhesive layer is a monolayer structure in the
embodiment described above, the adhesive layer may be a multilayer
structure. An adhesive layer having a multilayer structure may be
formed by coating an adhesive composition stepwise by any one of
the known techniques described above before irradiation with active
rays or radiation; or coating an adhesive composition by any one of
the known techniques described above after irradiation with active
rays or radiation or the like. In an embodiment comprising an
adhesive layer having a multilayer structure wherein the adhesive
layer 11 is an adhesive layer having adhesiveness that decreases by
irradiation with active rays or radiation or heat, for example, the
adhesiveness of the adhesive layer as a whole can be decreased by
decreasing adhesion between layers by irradiation with active rays
or radiation or heat.
[0268] Further, the member to be processed supported on the
adhesive support is not limited to a silicon substrate as mentioned
in the embodiment described above, but may be any member to be
processed capable of being subjected to a mechanical or chemical
process during manufacturing processes of semiconductor
devices.
[0269] For example, the member to be processed may also be a
compound semiconductor substrate, and specific examples of compound
semiconductor substrates include SiC substrates, SiGe substrates,
ZnS substrates, ZnSe substrates, GaAs substrates, InP substrates,
and GaN substrates and the like.
[0270] Further, the mechanical or chemical process of the silicon
substrate supported by the adhesive support is not limited to
thinning of the silicon substrate and formation of through-silicon
vias as mentioned in the embodiment described above, but may be any
necessary process in manufacturing processes of semiconductor
devices.
[0271] Further, the shape, size, number, location and the like of
the light-transmitting regions and light-shielding regions in the
mask, the high adhesion regions and low adhesion regions in the
adhesive layer, and the device chips in the device wafer are not
limited to the examples shown in the embodiment described above,
but may be any values so far as the present invention can be
achieved.
EXAMPLES
[0272] The following examples further illustrate the present
invention, but the present invention is not limited to these
examples and changes may be made without departing from the spirit
of the invention. Unless otherwise specified, "parts" and "%" are
based on mass.
<Formation of an Adhesive Support (Adhesive Layer (B))>
[0273] A 4-inch Si wafer was coated with each liquid adhesive
composition consisting of the components shown in Table 1 below
using a spin coater (Opticoat MS-A100 from Mikasa, 1200 rpm, 30
seconds), and then baked under the baking conditions described in
Table 1 to form a wafer 1 provided with an adhesive layer having a
thickness of 10 .mu.m (i.e., an adhesive support). Then, the
adhesive layer was exposed at 2000 mJ/cm.sup.2 to produce a
halftone image by irradiation from the side of the adhesive layer
of the wafer 1 using a UV exposure system (LC8 from Hamamatsu
Photonics K.K.) through a photomask having a halftone pattern
consisting of light-transmitting regions and light-shielding
regions wherein the light-shielding regions are dot regions in the
halftone pattern. Exposure was performed while the shape of each
dot region (light-shielding region) of the photomask was changed as
shown in Table 3 in each Example (Table 3 also shows the area rate
of light-transmitting regions in each photomask). The pattern
formed by dot regions (high adhesion regions) on the surface of the
adhesive layer is a pattern as shown in FIG. 4.
TABLE-US-00001 TABLE 1 Thermal Polymerizable polymerization Binder
monomer Photoinitiator initiator Solvent Content Content Content
Content Content Baking Type (parts) Type (parts) Type (parts) Type
(parts) Type (parts) conditions Adhesive Resin 50 Polymerizable 50
Photoinitiator 5 Thermal 5 S1 150 100.degree. C. composition 1 (1)
monomer (1) (1) polymerization 30 seconds initiator (1) Adhesive
Resin 50 Polymerizable 50 Photoinitiator 5 Thermal 5 S2 150
100.degree. C. composition 2 (1) monomer (2) (1) polymerization 30
seconds initiator (1) Adhesive Resin 50 Polymerizable 50
Photoinitiator 5 Thermal 5 S3 150 100.degree. C. composition 3 (2)
monomer (1) (1) polymerization 30 seconds initiator (1) Adhesive
Resin 10 none -- none -- none -- S4 100 100.degree. C. composition
4 (3) 60 seconds Resin 50 (4)
[0274] The compounds described in Table 1 are as follows.
<Binders>
[0275] Resin (1): ESTYRENE MS200NT (an MS resin from Nippon Steel
Chemical Co., Ltd.) [0276] Resin (2): ZEONEX 480R (a cycloolefin
resin from Zeon Corporation) [0277] Resin (3): Buna EP T6250 (an
ethylene-propylene terpolymer rubber from LANXESS) [0278] Resin
(4): Eastotac H-142W (a hydrocarbon resin from Eastman Chemical
Company)
<Polymerizable Monomers>
[0278] [0279] Polymerizable monomer (1): A-DCP (a bifunctional
acrylate from Shin-Nakamura Chemical Co., Ltd.) [0280]
Polymerizable monomer (2): A-BPE-4 (a bifunctional acrylate from
Shin-Nakamura Chemical Co., Ltd.)
<Photoinitiator>
[0280] [0281] Photoinitiator (1): KAYACURE DETX-S
(2,4-dimethylthioxanthone from Nippon Kayaku Co., Ltd.) ps
<Thermal Polymerization Initiator> [0282] Thermal
polymerization initiator (1): PERBUTYL Z (tert-butyl peroxybenzoate
from NOF CORPORATION)
<Solvents>
[0282] [0283] S1: Methyl amyl ketone [0284] S2: PGMEA (propylene
glycol 1-monomethyl ether 2-acetate) [0285] S3: Limonene [0286] S4:
1-Dodecene
<Preparation of a Processed Member (Release Layer (A))>
[0287] A 4-inch Si wafer provided with Cu electrodes having a
height of 10 .mu.m and a diameter of 50 .mu.m spaced 200 .mu.m
apart on its surface was coated with each release layer composition
consisting of a mixture of the resin 1 solution shown in Table 2
below and the resin 2 solution shown in Table 3 in the ratio shown
in Table 4 on the side having these electrodes using a spin coater
(Opticoat MS-A100 from Mikasa, 1200 rpm, 30 seconds), and then
baked under the conditions described in Table 4 to form a wafer 2
provided with a release layer having a thickness of 20 .mu.m.
Baking was performed in two stages. Specifically, a first stage of
baking was performed at the temperature and for the time described
in each upper row in Table 4, and a second stage of baking was
performed at the temperature and for the time described in each
lower row in Table 4.
[0288] The softening point of the resin 1 was determined using the
viscoelastometer Rheosol-G5000 (from UBM). Specifically, the
softening point of the resin 1 is determined as the temperature at
which the loss tangent (tan .delta.) measured using a
viscoelastometer under predetermined heating conditions is maximum.
In the Examples, it was determined using the viscoelastometer
Rheosol-G5000 when the temperature of the resin 1 formed into a
50-.mu.m film was raised from 25.degree. C. to 500.degree. C. at a
heating rate of 5.degree. C./min and a strain of an angle of
0.05.degree. was applied to the resin 1 at a frequency of 1 Hz.
[0289] The SP values of the resins were estimated by the Okitsu
method.
TABLE-US-00002 TABLE 2 Resin 1 Solvents Content Content Resin 1
solution Type (%) Type (%) Resin solution 1-1 Resin (1-1) 20
N-methyl-2- 80 pyrrolidone(NMP) Resin solution 1-2 Resin (1-2) 20
N-ethyl-2- 80 pyrrolidone Resin solution 1-3 Resin (1-3) 20 N,N- 80
dimethylacetamide Resin solution 1-4 Resin (1-4) 20 NMP 80 Resin
solution 1-5 Resin (1-5) 20 p-xylene 80 Resin solution 1-6 Resin
(1-6) 20 p-xylene 80 Resin solution 1-7 Resin (1-7) 20 NMP 80
[0290] Resin (1-1): Durimide 10 (a solvent-soluble polyimide resin
having a softening point of 310.degree. C. and an SP value >25
from Fujifilm) [0291] Resin (1-2): Ultrason E6020 (a polyether
sulfone resin having a softening point of 240.degree. C. and an SP
value >25 from BASF) [0292] Resin (1-3): MRS0810H (a
polybenzimidazole resin having a softening point of 430.degree. C.
and an SP value >25 from SATO LIGHT INDUSTRIAL Co., LTD.) [0293]
Resin (1-4): RIKACOAT (a solvent-soluble polyimide resin having a
softening point of 320.degree. C. and an SP value >25 from New
Japan Chemical Co., Ltd.) [0294] Resin (1-5): Xyron S201A (a
polyphenylene ether resin having a softening point of 220.degree.
C. and an SP value of 20 from Asahi Kasei Chemicals Corp.) [0295]
Resin (1-6): Polystyrene Mw=280,000 (a polystyrene resin having a
softening point of 120.degree. C. and an SP value of 20 from
Sigma-Aldrich Japan K.K.) [0296] Resin (1-7): Maranyl nylon 66
A125J (a polyamide resin having a softening point of 220.degree. C.
and an SP value >28 from Unitika Limited)
TABLE-US-00003 [0296] TABLE 3 Resin 2 Solvents Content Content
Resin 2 solution Type (%) Type (%) Resin solution 2-1 Resin (2-1)
20 THF 80 Resin solution 2-2 Resin (2-2) 20 Cyclohexanone 80 Resin
solution 2-3 Resin (2-3) 20 PGMEA 80 Resin solution 2-4 Resin (2-4)
20 Methyl amyl ketone 80 Resin solution 2-5 Resin (2-5) 20
Xylene/N-methyl-2- 80 pyrrolidone[20% by mass/80% by mass]
[0297] Resin (2-1): TOPAS 5013 (having an SP value of 18 from
Polyplastics Co., Ltd.) [0298] Resin (2-2): Panlite L-1225LM (a
polycarbonate resin having an SP value of 22 from TEIJIN LIMITED)
[0299] Resin (2-3): ESTYRENE MS200NT (an MS resin having an SP
value of 18 from NIPPON STEEL & SUMIKIN CHEMICAL CO., LTD.)
[0300] Resin (2-4): L-70 (a cellulose acetate resin having an SP
value of 21 from Daicel Corporation) [0301] Resin (2-5): VYLOMAX
HR-13NX (a polyamide-imide resin having an SP value >25 that
becomes solvent-insoluble upon baking from TOYOBO CO., LTD.)
TABLE-US-00004 [0301] TABLE 4 Resin 1 solution Resin 2 solution
Liquid release layer Content Content composition Type (%) Type (%)
Baking conditions Release layer 1 Resin solution 100 None 0
100.degree. C. 10 minuets 1-1 250.degree. C. 10 minuets Release
layer 2 None 0 Resin 100 100.degree. C. 10 minuets solution2-3
170.degree. C. 10 minuets Release layer 3 Resin 80 Resin 20
100.degree. C. 10 minuets solution1-1 solution2-5 250.degree. C. 10
minuets Release layer 4 Resin 75 Resin 25 100.degree. C. 5 minuets
solution1-6 solution2-3 180.degree. C. 10 minuets Release layer 5
Resin 75 Resin 25 100.degree. C. 10 minuets solution1-1 solution2-3
250.degree. C. 10 minuets Release layer 6 Resin 85 Resin 15
100.degree. C. 10 minuets solution1-1 solution2-3 250.degree. C. 10
minuets Release layer 7 Resin 75 Resin 25 100.degree. C. 10 minuets
solution1-1 solution2-1 250.degree. C. 10 minuets Release layer 8
Resin 50 Resin 50 100.degree. C. 10 minuets solution1-1 solution2-2
250.degree. C. 10 minuets Release layer 9 Resin 80 Resin 20
100.degree. C. 10 minuets solution1-1 solution2-3 250.degree. C. 10
minuets Release layer 10 Resin 90 Resin 10 100.degree. C. 10
minuets solution1-1 solution2-4 250.degree. C. 10 minuets Release
layer 11 Resin 80 Resin 20 100.degree. C. 10 minuets solution1-2
solution2-3 250.degree. C. 10 minuets Release layer 12 Resin 80
Resin 20 100.degree. C. 10 minuets solution1-3 solution2-3
200.degree. C. 10 minuets Release layer 13 Resin 80 Resin 20
100.degree. C. 10 minuets solution1-4 solution2-3 250.degree. C. 10
minuets Release layer 14 Resin 99 Resin 1 100.degree. C. 5 minuets
solution1-5 solution2-3 180.degree. C. 10 minuets Release layer 15
Resin 99 Resin 1 100.degree. C. 5 minuets solution1-7 solution2-1
180.degree. C. 10 minuets
<Preparation of Adhesion Test Specimens>
[0302] Test specimens were prepared by bonding the wafer 1 and the
wafer 2 in each combination described in Table 5 or 6 below under
heat and pressure.
<<Pressure Bonding>>
[0303] A 4-inch Si wafer having no coating on the surface or a
4-inch Si wafer provided with a release layer (hereinafter referred
to as wafer 2) was divided into sample pieces of 20 mm.times.30 mm.
The wafer 1 was divided into sample pieces of 20 mm.times.30 mm in
the same manner, and both sample pieces were superposed in such a
manner that the adhesive layer comes into contact with the wafer
having no coating on the surface or the release layer of the wafer
2 in a square of 20 mm.times.20 mm and bonded under heat and
pressure at 1 N/cm.sup.2 and 120.degree. C. for 3 minutes.
<Determination of the Bond Strength of the Laminate Test
Specimens>
[0304] The prepared test specimens were measured for their shear
bond strength using a tensile tester (from IMADA CO., LTD.) in a
direction along the plane of the adhesive layer under the
conditions of 250 mm/min. The results are shown in Table 5 or 6
below.
<Determination of the Peel Strength and Peel Strength After
Heating of the Laminate Test Specimens>
[0305] The prepared sample pieces were subjected to a tensile test
in a direction perpendicular to the plane of the adhesive layer
under the conditions of 250 mm/min (determination of peel
strength). Further, the prepared sample pieces were heated at each
temperature described in Table 5 or 6 for 30 minutes, and then
subjected to a tensile test in a direction perpendicular to the
plane of the adhesive layer under the conditions of 250 mm/min
(determination of peel strength after heating under conditions
mimic to the maximum attainable temperature of the process). The
results are shown in Table 5 or 6 below.
<Evaluation of the Removal of the Bonding Layers of the Laminate
Test Specimens>
[0306] After the prepared sample pieces were separated, the wafer 2
was immersed in each solvent described in Table 5 or 6, and the
time required for both of the adhesive layer and the release layer
to be removed from the wafer 2 was determined. The results are
shown in Table 5 or 6.
TABLE-US-00005 TABLE 5 Peel strength after heating Abundance
Maximum Peel Removal of halftone attainable strength Removal
Peeling Adhesive Shape of dots Bond Peel temperature after Peeling
tine layer Release layer halftone dots (%) strength strength
(.degree. C.) heating solvent (minuets) Comparative Adhesive
Release layer Not exposure Adhesion 50 8 180 8 NMP >60 Example 1
composition 1 on entire 1 surface Comparative Adhesive Release
layer Each side of 4% 50 8 180 18 THF 20 Example 2 composition 2
Square is 1 mm. Wafer 1 Area 1 mm.sup.2 cracking Comparative
Adhesive Release layer Not exposure Adhesion 50 8 200 8 NMP >60
Example 3 composition 3 on entire 1 surface Comparative Adhesive
Release layer Each side of 4% 50 3 200 20 THF 20 Example 4
composition 4 Square is 1 mm. Wafer 1 Area 1 mm.sup.2 cracking
Comparative Adhesive None Each side of Square is 4% 50 25 200 25
NMP >60 Example 5 composition 1 mm. Wafer Wafer 1 Area 1
mm.sup.2 cracking cracking Comparative None Release layer None -- 0
-- -- -- -- Example 6 5 Example 1 Adhesive Release layer Not
exposure Adhesion 50 6 200 6 THF 20 composition 7 on entire 1
surface Example 2 Adhesive Release layer Circle Diameter 3% 40 2
200 3 1,3- 15 composition 8 1 mm dioxolane 2 Area 0.785 mm.sup.2
Example 3 Adhesive Release layer Each side of 3% 50 2 200 5 THF 20
composition 9 Square is 1 mm. 3 Area 1 mm.sup.2 Example 4 Adhesive
Release layer Each side of 3% 50 2 200 3 Acetone 25 composition 10
Square is 1 mm. 1 Area 1 mm.sup.2
TABLE-US-00006 TABLE 6 Peel strength after heating Abundance
Maximum Peel of halftone attainable strength Removal Removal
Adhesive Release Shape of dots Bond Peel temperature after Peeling
Peeling tine layer layer halftone dots (%) strength strength
(.degree. C.) heating solvent (minuets) Example 5 Adhesive Release
layer Not exposure Adhesion on 50 3 200 3 Anisole 20 composition 2
11 entire surface Example 6 Adhesive Release layer Each side of 4%
50 3 370 3 1,3- 10 composition 3 12 Square is 1 mm. dioxolane Area
1 mm.sup.2 Example 7 Adhesive Release layer Each side of 4% 50 5
300 3 Toluene 25 composition 1 13 Square is 1 mm. Area 1 mm.sup.2
Example 8 Adhesive Release layer Each side of 4% 50 3 200 3 THF 20
composition 2 14 Square is 1 mm. Area 1 mm.sup.2 Example 9 Adhesive
Release layer Not exposure 4% 50 7 200 7 THF 20 composition 4 14
Example 10 Adhesive Release layer Not exposure Adhesion on 50 3 180
3 Anisole 20 composition 2 11 entire surface Example 11 Adhesive
Release layer Not exposure Adhesion on 50 3 220 3 Anisole 20
composition 2 11 entire surface Example 12 Adhesive Release layer
Not exposure Adhesion on 50 3 230 6 Anisole 20 composition 2 11
entire surface Example 13 Adhesive Release layer Not exposure
Adhesion on 50 7 200 8 THF 30 composition 2 15 entire surface
[0307] In the tables above, the abundance of halftone dots is
expressed in %, and the bond strength, peel strength and peel
strength after heating are expressed in N/25 mm.sup.2.
[0308] The results above show that Comparative example 1 not
comprising the resin 2 exhibited adhesiveness and releasability but
insufficient removability; Comparative example 2 not comprising the
resin 1 exhibited insufficient releasability; Comparative example 3
comprising a release layer and an adhesive layer wherein the resin
2 is solvent-insoluble exhibited adhesiveness and releasability but
insufficient removability; Comparative example 4 comprising a
release layer and an adhesive layer wherein the resin 1 does not
have a softening point of 200.degree. C. or more exhibited
adhesiveness but insufficient removability; Comparative example 5
not comprising a release layer exhibited insufficient
releasability; and Comparative example 6 not comprising an adhesive
layer exhibited insufficient adhesiveness. In contrast, Examples 1
to 12 were shown to achieve adhesiveness, releasability and
removability at the same time even after a high temperature process
(more specifically at 180.degree. C. to 370.degree. C.) because the
temporary bonding laminates of the present invention are
characterized in that the resin 1 has a softening point of
200.degree. C. or more, the resin 2 is solvent-soluble and the
adhesive layer has two or more regions of different bond strengths
on its surface obtained by exposing the surface of a layer having
an adhesiveness that increases or decreases when irradiated with
active rays or radiation.
DESCRIPTION OF THE REFERENCE NUMERALS
[0309] 2: resin 2; [0310] 11, 21 to 30, 11': adhesive layer; [0311]
11A, 21A to 30A: high adhesion regions; [0312] 11B, 21B to 30B: low
adhesion regions; [0313] 12: carrier substrate; [0314] 60: device
wafer; [0315] 60': thinned device wafer; [0316] 61: silicon
substrate [0317] 61a: frontside of the silicon substrate; [0318]
61b: backside of the silicon substrate; [0319] 61b': backside of
the thinned device wafer; [0320] 62: device chips; [0321] 63:
bumps; [0322] 70: tape; [0323] 71: release layer; [0324] 1,71:
release layer [0325] 80: temporary bonding laminate; [0326] 100,
100': adhesive support.
* * * * *